Pyrazde herbicides

ABSTRACT

Compounds of the formula I                    
     in which 
     R 1  is C 1 -C 4 alkyl; 
     R 2  is cyano or NH 2 C(S)—; 
     R 3  is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 - or C 4 alkenyl, C 3 - or C 4 alkynyl, C 3 -C 8 haloalkenyl, NC—CH 2 —, HOC(O)—CH 2 — or C 1 -C 4 alkoxy-C(O)—CH 2 —; 
     W is a group                    
      and 
     R 4  to R 6 , R 60 , R 61 , R 70 , X 1 , X 2 , n 1  and A 1 —B 1  are as defined in claim 1, and the pyrazole N-oxide, agronomically acceptable salts and stereomers of these compounds of the formula I, with the exclusion of the compound of the formula                    
      have good selective herbicidal properties when used pre- and post-emergence. The preparation of these compounds and their use as herbicidally active ingredients are described.

The present invention relates to novel herbicidally active substituted pyrazole derivatives, to processes for their preparation, to compositions comprising these compounds, and to their use for controlling weeds, in particular in crops of useful plants, for example cereals, maize, rice, cotton, soya, oilseed rape, sorghum, sugar cane, sugar beet, sunflowers, vegetables and fodder plants, or for inhibiting the growth of plants.

Herbicidally active pyrozole compounds have been disclosed and are described, for example, in JP-A-03 093 774, JP-A-02 300 173, JP-A-03 072 460, EP-A-0 361 114 and WO 96/01254.

There have now been found novel substituted pyrazole derivatives which have herbicidal and growth-inhibiting properties.

The present invention thus relates to compounds of the formula I

in which

R₁ is C₁-C₄alkyl;

R₂ is cyano or NH₂C(S)—;

R₃ is hydrogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₃- or C₄alkenyl, C₃- or C₄alkynyl, C₃-C₈haloalkenyl, NC—CH₂—, HOC(O)—CH₂- or C₁-C₄alkoxy-C(O)—CH₂—;

W is a group

R₄ is hydrogen, fluorine, chlorine, bromine or methyl;

R₅ is hydrogen, halogen, methyl, ethyl, cyano, trifluoromethyl, nitro, amino, hydroxy, C₁-C₄haloalkoxy, HOC(O)—C₁-C₄alkoxy, CIC(O)—C₁-C₄alkoxy, C₁-C₄alkoxycarbonyl-C₁-C₄alkoxy, mercapto, C₁-C₄alkylthio, HOC(O)—C₁-C₄alkylthio, C₁-C₄alkoxycarbonyl-C₁-C₄alkylthio, benzyloxy or benzyloxy which is mono- to trisubstituted by halogen, C₁-C₄alkyl or C₁-C₄haloalkyl;

R₆ is hydrogen, halogen, cyano, nitro, amino, CIS(O)₂—, R₁₀NH or R₁₀R₁₁N;

R₁₀ and R₁₁ independently of one another are C₁-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, C₃-C₆cycloalkyl, C₁-C₈haloalkyl, C₃-C₈haloalkenyl, C₁-C₄alkylcarbonyl, C₁-C₄haloalkylcarbonyl, C₁-C₄alkylsulfonyl, C₁-C₄haloalkylsulfonyl, benzoyl, benzoyl which is mono- to trisubstituted by C₁-C₄alkyl, C₁-C₄haloalkyl or halogen, or are benzyl or benzyl which is mono- to trisubstituted by C₁-C₄alkyl, C₁-C₄haloalkyl or halogen; or

R₆ is —OR₂₀;

R₂₀ is hydrogen, C₁-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, C₁-C₈haloalkyl,

 C₃-C₈haloalkenyl, C₃-C₆cycloalkyl,

 C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkenyloxy-C₁-C₄alkyl, C₁-C₄alkylamino-C₁-C₄alkyl, di-C₁-C₄alkylamino-C₁-C₄alkyl, C₁-C₄alkoxy-C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkylthio-C₁-C₄alkyl, C₁-C₄alkyl-C(O)—C₁-C₈alkyl,

 C₁-C₄alkyl-C(O—C₁-C₄alkyl)₂-C₁-C₈alkyl,

 phenyl, benzyl, pyridyl, pyrimidinyl, pyrazinyl or

 pyridazinyl, it being possible for these abovementioned aromatic and heteroaromatic rings to be mono- to trisubstituted by C₁-C₄alkyl, C₁-C₄haloalkyl or halogen; or

R₂₀ is R₂₁XC(O)—C₁-C₈alkyl or

X is oxygen, sulfur, or R₂₂N;

R₂₁ is hydrogen, C₁-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, C₁-C₈haloalkyl, C₃-C₆cycloalkyl, C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkylthio-C₁-C₄alkyl, phenyl, phenyl which is mono- to trisubstituted by C₁-C₄alkyl, C₁-C₄haloalkyl or halogen, or is benzyl or benzyl which is mono- to trisubstituted by C₁-C₄alkyl or halogen; and

R₂₂ is hydrogen, C₁-C₈alkyl or C₃-C₈alkenyl, or

R₆ is —S(O)_(m)R₃₀;

m is 0, 1 or 2;

R₃₀ is hydrogen, C₁-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, C₁-C₈haloalkyl, C₃-C₈haloalkenyl, C₃-C₆cycloalkyl, C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkylthio-C₁-C₄alkyl, C₁-C₄alkylC(O)—C₁-C₈alkyl, phenyl, phenyl which is mono- to trisubstituted by C₁-C₄alkyl, C₁-C₄haloalkyl or halogen, benzyl, benzyl which is mono- to trisubstituted by C₁-C₄alkyl, C₁-C₄haloalkyl or halogen, or R₃₁VC(O)—C₁-C₄alkyl;

V is oxygen, sulfur or R₃₂N;

R₃₁ is hydrogen, C₁-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, C₁-C₈haloalkyl, C₃-C₆cycloalkyl, C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkylthio-C₁-C₄alkyl, phenyl, phenyl which is mono- to trisubstituted by C₁-C₄alkyl, C₁-C₄haloalkyl or halogen, or is benzyl, or benzyl which is mono- to trisubstituted by C₁-C₄alkyl, C₁-C₄haloalkyl or halogen;

R₃₂ is hydrogen, C₁-C₈alkyl or C₃-C₈alkenyl; or

R₃₃ is hydrogen, C₁-C₈alkyl, C₃-C₈alkenyl or C₃-C₈alkynyl;

R₃₄ is hydrogen, C₁-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl or C₁-C₄alkylcarbonyl; or

R₆ is —COR₄₀;

R₄₀ is hydrogen, chlorine, C₁-C₈alkyl, C₂-C₈alkenyl, C₂-C₈alkynyl, C₁-C₈haloalkyl, C₂-C₈haloalkenyl, C₃-C₆cycloalkyl, C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkylthio-C₁-C₄alkyl, phenyl, phenyl which is mono- to trisubstituted by C₁-C₄alkyl, C₁-C₄haloalkyl or halogen, or is benzyl or benzyl which is mono- to trisubstituted by C₁-C₄alkyl, C₁-C₄haloalkyl or halogen; or

R₆ is —COYR₅₀;

Y is oxygen, sulfur, R₅₁N or R₅₄ON;

R₅₀ is hydrogen, C₁-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, C₁-C₈haloalkyl,

 C₃-C₈haloalkenyl, cyano-C₁-C₄alkyl, C₃-C₆cycloalkyl,

 C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkylthio-C₁-C₄alkyl, phenyl,

 phenyl which is mono- to trisubstituted by C₁-C₄alkyl, C₁-C₄haloalkyl or halogen, benzyl, benzyl which is mono- to trisubstituted by C₁-C₄alkyl, C₁-C₄haloalkyl or halogen, or is C₁-C₈alkylcarbonyl-C₁-C₄alkyl, R₅₂ZC(O)—C₁-C₆alkyl or R₅₂ZC(O)—C₃-C₆cycloalkyl;

Z is oxygen, sulfur, R₅₃N or R₅₅ON;

R₅₂ is hydrogen, C₁-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, C₁-C₈haloalkyl,

 C₃-C₈haloalkenyl, C₃-C₆cycloalkyl,

 C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkoxy-C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkylthio-C₁-C₄alkyl, phenyl, phenyl which is mono- to trisubstituted by C₁-C₄alkyl, C₁-C₄haloalkyl or halogen, or is benzyl or benzyl which is mono- to trisubstituted by C₁-C₄alkyl, C₁-C₄haloalkyl or halogen;

R₅₁ and R₅₃ independently of one another are C₁-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, C₁-C₈haloalkyl, C₁-C₄alkylcarbonyl, C₁-C₄haloalkylcarbonyl, C₁-C₄alkylsulfonyl, C₁-C₄haloalkylsulfonyl, benzoyl, benzoyl which is mono- to trisubstituted by C₁-C₄alkyl, C₁-C₄haloalkyl or halogen, or are benzyl or benzyl which is mono- to trisubstituted by C₁-C₄alkyl, C₁-C₄haloalkyl or halogen;

R₅₄ and R₅₅ independently of one another are C₁-C₄alkyl; or

R₆ is B—C₁-C₈alkyl, B—C₁-C₈haloalkyl, B—C₂-C₈alkenyl, B—C₂-C₈alkynyl, B—C₂-C₈haloalkenyl, B—C₁-C₄alkoxy-C₁-C₄alkyl or B—C₁-C₄alkylthio-C₁-C₄alkyl; and

B is hydrogen, R₅₂ZC(O)—, cyano or C₁-C₄alkylcarbonyl;

X₁ and X₂ independently of one another are oxygen or sulfur;

R₆₀ is hydrogen or C₁-C₄alkyl;

R₆₁ is hydrogen, C₁-C₆alkyl, C₃-C₆cycloalkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, benzyl, benzyl substituted by halogen, C₁-C₆haloalkyl, C₃-C₆haloalkenyl, C₁-C₄alkyl-C(O)—C₁-C₄alkyl, C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkoxy-C₁-C₄alkoxy-C₁-C₄alkyl, HOC(O)—C₁-C₆alkyl, CIC(O)—C₁-C₆alkyl, C₁-C₆alkoxycarbonyl-C₁-C₆alkyl, C₁-C₆haloalkoxycarbonyl-C₁-C₆alkyl, C₃-C₆alkenyloxycarbonyl-C₁-C₆alkyl, C₃-C₆alkynyloxycarbonyl-C₁-C₆alkyl, C₁-C₆alkylthio-C(O)—C₁-C₆alkyl, C₃-C₆alkenylthio-C(O)—C₁-C₆alkyl, C₃-C₆alkynylthio-C(O)—C₁-C₆alkyl, C₁-C₆haloalkylthio-C(O)—C₁-C₆alkyl,

R₆₂R₆₃NC(O)—C₁-C₆alkyl,

 C₁-C₄alkoxycarbonyl, C₃-C₆alkenyloxycarbonyl, C₃-C₆alkynyloxycarbonyl, oxetanyloxycarbonyl, HOC(O)—C₃-C₆cycloalkyl, C₁-C₄alkoxycarbonyl-C₃-C₆cycloalkyl, C₃-C₆alkenyloxycarbonyl-C₃-C₆cycloalkyl, C₃-C₆alkynyloxycarbonyl-C₃-C₆cycloalkyl, C₁-C₆alkylthio-C₁-C₆alkyl, C₃-C₆alkenylthio-C(O)—C₃-C₆cycloalkyl or CIC(O)—C₃-C₆cycloalkyl;

R₆₂ is hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₆haloalkyl, benzyl, phenyl, or phenyl which is mono- to trisubstituted by halogen, C₁-C₄alkyl or C₁-C₄haloalkyl;

R₆₃ has the meaning of R₆₂, or is C₃-C₆cycloalkyl, C₃-C₆halocycloalkyl, phenyl or phenyl which is mono- to trisubstituted by halogen, C₁-C₄alkyl or C₁-C₄haloalkyl;

n₁ is 0, 1, 2, 3 or 4;

R₇₀ is hydrogen, halogen, trifluoromethyl, cyano, nitro, amino or C₁-C₄haloalkoxy;

A₁—B₁ is a group

 the carbon atom 2 being bonded to the oxygen atom;

R₇₁ is hydrogen or C₁-C₆alkyl;

R₇₂ is hydrogen, cyano, C₁-C₆alkyl, C₁-C₆haloalkyl, cyano-C₁-C₄alkyl, hydroxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl, C₃-C₆alkenyloxy-C₁-C₄alkyl, C₃-C₆alkynyloxy-C₁-C₄alkyl, C₁-C₆alkylcarbonyloxy-C₁-C₆alkyl, C₁-C₆alkoxycarbonyl-C₁-C₆alkyl, HOC(O)—C₁-C₆alkyl, CIC(O)—C₁-C₆alkyl, carboxyl, CIC(O)—C₁-C₆alkoxycarbonyl, C₁-C₆haloalkoxycarbonyl, C₃-C₆alkenyloxycarbonyl, C₃-C₆alkynyloxycarbonyl, C₃-C₆cycloalkoxycarbonyl, C₁-C₆alkoxy-C₁-C₆alkoxycarbonyl, benzyloxycarbonyl, benzyloxycarbonyl which is mono- to trisubstituted by halogen, or is C₁-C₄alkoxycarbonyl, HOC(S)—, C₁-C₆alkylthio-C(O)—, C₁--C₆haloalkylthio-C(O)—, C₃-C₆alkenylthio-C(O)—, C₃-C₆alkynylthio-C(O)—, benzylthio-C(O)—, benzyl, benzyl which is mono- to trisubstituted by halogen, or is R₇₃R₇₄NC(O)—, phenoxycarbonyl or phenyl-C₁-C₆alkyl, it being possible for the phenyl ring to be substituted by halogen, C₁-C₄alkyl or C₁-C₄haloalkyl, or is NH₂C(S)— or OHC—;

R₇₃ is hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, benzyl, benzyl which is mono- to trisubstituted by halogen, C₁-C₄alkyl or C₁-C₄haloalkyl, or is C₁-C₆haloalkyl; and R₇₄ has the meaning of R₇₃, or is phenyl or phenyl which is mono- to trisubstituted by halogen, C₁-C₄alkyl or C₁-C₄haloalkyl, and the pyrazole N-oxides, agronomically acceptable salts and stereoisomers of these compounds of the formula I, with the exclusion of the compound of the formula

In the definitions mentioned above, halogen is to be understood as meaning iodine, and preferably fluorine, chlorine and bromine.

The alkyl, alkenyl and alkynyl groups in the definitions of the substitutents can be straight-chain or branched, and this also applies to the alkyl, alkenyl and alkynyl moiety of the alkylcarbonyl, hydroxyalkyl, cyanoalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, alkylthio, alkylthio-C(O), alkenylthio-C(O), alkynylthio-C(O), alkylsulfonyl, alkylaminoalkyl, dialkylaminoalkyl, alkylcarbonylalkyl, B—C₁-C₈alkyl, B—C₂-C₈alkenyl, B—C₂-C₈alkynyl, HOC(O)—C₁-C₆alkyl, CIC(O)—C₁-C₆alkyl, phenyl-C₁-C₆alkyl, alkylcarbonyloxyalkyl, R₂₁XC(O)—C₁-C₈alkyl, R₃₁VC(O)—C₁-C₄alkyl, R₅₂ZC(O)—C₁-C₆alkyl and R₆₂R₆₃N—C(O)—C₁-C₆alkyl groups.

Alkyl groups are, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl and the various isomeric pentyl, hexyl, heptyl and octyl radicals. Methyl, ethyl, n-propyl, iso-propyl and n-butyl are preferred. For example, R₁ is n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, preferably methyl and ethyl, and especially preferably methyl.

Examples of alkenyls which may be mentioned are vinyl, allyl, methallyl, 1-methylvinyl, but-2-en-1-yl, pentenyl, 2-hexenyl, 3-heptenyl and 4-octenyl, preferably alkenyl radicals having a chain length of 3 to 5 carbon atoms.

Examples of alkynyls which may be mentioned are ethynyl, propargyl, 1 -methylpropargyl, 3-butynyl, but-2-yn-1-yl, 2-methylbutyn-2-yl, but-3-yn-2-yl, 1-pentynyl, pent-4-yn-1-yl or 2-hexynyl, preferably alkynyl radicals having a chain length of 2 to 4 carbon atoms.

Suitable as haloalkyl are alkyl groups which are mono- or polysubstituted, in particular mono- to trisubstituted, by halogen, halogen specifically meaning iodine and in particular fluorine, chlorine and bromine, for example fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2-chloroethyl, 2,2-dichloroethyl, 2,2,2-trifluoroethyl and 2,2,2-trichloroethyl.

Cyanoalkyl is, for example, cyanomethyl, cyanoethyl, cyanoeth-1-yl and cyanopropyl.

Hydroxyalkyl is, for example, hydroxymethyl, 2-hydroxyethyl and 3-hydroxypropyl.

Alkenyloxyalkyl is, for example, allyloxyalkyl, methallyloxyalkyl and but-2-en-1-yloxyalkyl.

Alkynyloxyalkyl is, for example, propargyloxyalkyl and 1-methylpropargyloxyalkyl.

Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, iso-propoxycarbonyl and n-butoxycarbonyl, preferably methoxycarbonyl and ethoxycarbonyl.

Alkenyloxycarbonyl is, for example, allyloxycarbonyl, methallyloxycarbonyl, but-2-en-1-yl-oxycarbonyl, pentenyloxycarbonyl and 2-hexenyloxycarbonyl.

Alkynyloxycarbonyl is, for example, propargyloxycarbonyl, 3-butynyloxycarbonyl, but-2-yn-1-yloxycarbonyl and 2-methylbutyn-2-yloxycarbonyl.

Suitable as haloalkenyl are alkenyl groups which are mono- or polysubstituted by halogen, halogen specifically meaning bromine, iodine and in particular fluorine and chlorine, for example 2- and 3-fluoropropenyl, 2- and 3-chloropropenyl, 2- and 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl, 4,4,4-trifluorobut-2-en-1-yl and 4,4,4-trichlorobut-2-en-1-yl. Preferred amongst the alkenyl radicals which are mono-, di- or trisubstituted by halogen are those which have a chain length of 3 or 4 carbon atoms. The alkenyl groups on saturated or unsaturated carbon atoms can be substituted by halogen.

Alkoxyalkoxycarbonyl is, for example, methoxymethoxycarbonyl, ethoxymethoxycarbonyl, ethoxyethoxycarbonyl, propoxymethoxycarbonyl, propoxyethoxycarbonyl, propoxypropoxycarbonyl and butoxyethoxycarbonyl.

Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2,2-trichloroethoxy.

The cycloalkyl radicals which are suitable as substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

The cycloalkoxycarbonyl radicals which are suitable as substituents are, for example, cyclopropyloxycarbonyl, cyclobutyloxycarbonyl, cyclopentyloxycarbonyl and cyclohexyloxycarbonyl.

The halocycloalkyl radicals which are suitable as substituents are, for example, mono-, di- or up to perhalogenated cycloalkyl radicals, for example fluorocyclopropyl, 2,2-dichlorocyclopropyl, perfluorocyclopentyl or pentachlorocyclohexyl.

Alkoxyalkoxyalkyl is, for example, methoxymethoxymethyl, ethoxymethoxyethyl, ethoxyethoxymethyl, propoxymethoxymethyl,propoxyethoxyethyl, propoxypropoxymethyl, butoxyethoxyethyl and butoxybutoxyethyl.

Alkylthio is, for example, methylthio, ethylthio, propylthio and butylthio, and their branched isomers.

Alkylthioalkyl is, for example, methylthioethyl, ethylthioethyl, methylthiopropyl and ethylthiopropyl.

Alkylthiocarbonylalkyl is, for example, methylthiocarbonylalkyl, ethylthiocarbonylalkyl, n-propylthiocarbonylalkyl, iso-propylthiocarbonylalkyl and n-butylthiocarbonylalkyl.

Alkenylthiocarbonylalkyl is, for example, allylthiocarbonylalkyl, methallylthiocarbonylalkyl, but-2-en-1-yl-thiocarbonylalkyl, pentenylthiocarbonylalkyl and 2-hexenylthiocarbonylalkyl.

Alkynylthiocarbonylalkyl is, for example, propargylthiocarbonylalkyl, 1-methylpropargylthiocarbonylalkyl and but-2-yn-yl-thiocarbonylalkyl.

Haloalkylthio-C(O)— is, for example, fluoromethylthiocarbonyl, difluoromethylthiocarbonyl, trifluoromethylthiocarbonyl, 2,2,2-trifluoroethylthiocarbonyl, 1,1,2,2-tetrafluorethyfthiocarbonyl, 2-fluoroethylthiocarbonyl, 2-chloroethylthiocarbonyl and 2,2,2-trichloroethylthiocarbonyl.

Phenyl, benzyl or benzoyl as part of a substituent, for example phenoxy, phenylthio, benzyloxy, benzylthio, phenoxycarbonyl, benzyloxycarbonyl, phenoxycarbonylalkyl, benzyloxycarbonylalkyl, benzoylamino or benzylamino are in substituted or unsubstituted form. In this case, the substituents can be in the ortho, meta or para position. Examples of substituents are C₁-C₄alkyl, halogen or C₁-C₄haloalkyl.

Corresponding meanings can also be allocated to the substituents in composite definitions, for example alkoxy-C(O)—CH₂—, HOC(O)-alkoxy, CIC(O)-alkoxy, alkoxycarbonylalkoxy, HOC(O)-alkylthio, alkoxycarbonylalkylthio, haloalkylcarbonyl, haloalkylsulfonyl, R₅₂ZC(O)-cycloalkyl, B-haloalkyl, B-haloalkenyl, B-alkoxyalkyl, B-alkylthioalkyl, alkoxycarbonylalkyl, haloalkoxycarbonylalkyl, alkenyloxycarbonylalkyl, alkynyloxycarbonylcycloalkyl, alkenylthio-C(O)-cycloalkyl, CIC(O)-cycloalkyl, CIC(O)-alkoxycarbonyl, haloalkoxycarbonyl, alkynyloxycarbonylalkyl, haloalkylthio-C(O)-alkyl, HOC(O)-cycloalkyl, alkoxycarbonylcycloalkyl and alkenyloxycarbonylcycloalkyl.

In the definition of R₂₀, the group

means that the R₂₁XC(O)—substituted C₁-C₆alkylene chain is additionally substituted on one of the 6 carbon atoms by phenyl.

In the definition of R₆₁, the groups

and

means that the HOC(O)—, C₁-C₄alkoxy-C(O)—, C₃-C₆alkenyloxy-C(O)— or C₃-C₆alkynyloxy-C(O)— substituted C₁-C₆alkylene chain is additionally substituted on one of the 6 carbon atoms by phenyl (C₆H₅).

In the definitions cyanoalkyl, alkylcarbonyl, alkoxycarbonyl, haloalkylcarbonyl, alkylcarbonyloxy, alkoxyalkoxycarbonyl, alkylthiocarbonyl and cycloalkoxycarbonyl, the cyano or carbonyl carbon atom is not included in the lower and upper limitations of the number of carbon atoms given in each case.

A benzyloxy which is mono- to trisubstituted by halogen, C₁-C₄alkyl or C₁-C₄haloalkyl, for example in the definition of R₅, means that the aromatic ring is substituted by halogen, C₁-C₄alkyl or C₁-C₄haloalkyl. The same applies to benzyl and benzyloxycarbonyl which are mono- to trisubstituted, for example in the definition of R₁₀, R₁₁ and R₇₂.

The compounds of the formula I are generally present in the form of mixtures composed of the isomers Ia and Ib

which are substituted in the 3- and 5-position of the pyrazole ring by the group W. The isomeric ratio Ia/Ib may vary, depending on the synthesis process.

Also part of the invention are the salts which those compounds of the formula I which have an acidic hydrogen, in particular the derivatives which have carboxylic acid and sulfonamide groups (for example carboxyl-substituted alkyl, alkylene, alkoxy, alkylthio, cycloalkyl and phenyl groups and NH₂SO₂-substituted phenyl groups) can form with bases. These salts are, for example, alkali metal salts, for example sodium salts and potassium salts; alkaline earth metal salts, for example calcium salts and magnesium salts; ammonium salts, i.e. unsubstituted ammonium salts and mono- or polysubstituted ammonium salts, for example triethylammonium salts and methylammonium salts; or salts with other organic bases.

Substances which are important amongst the alkali metal hydroxides and alkaline earth metal hydroxides as salt formers are, for example, the hydroxides of lithium, sodium, potassium, magnesium or calcium, but in particular those of sodium and potassium.

Possible examples of amines which are suitable for ammonium salt formation are ammonia and also primary, secondary and tertiary C₁-C₈alkylamines, C₁-C₄hydroxyalkylamines and C₂-C₄alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomeric butylamines, n-amylamine, iso-amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methyl-isopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n-propylamine, di-isopropylamine, di-n-butylamine, di-n-amylamine, di-isoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, di-butenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, tri-isopropylamine, tri-n-butylamine, tri-isobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, thiomorpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o,m,p-toluidines, phenylenediamines, benzidines, naphthylamines and o,m,p-chloroanilines; but in particular triethylamine, isopropylamine and di-isopropylamine.

The salts of the compounds of the formula I which have basic groups, in particular basic pyridyl, pyrimidinyl and pyrazolyl rings or of the derivatives with amino groups, for example, alkylamino and dialkylamino groups in the definition of R₂₀, or aniline derivatives where R₅, R₆ or R₇₀=amino are, for example, salts with inorganic and organic acids, for example hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid, and also sulfuric acid, phosphoric acid, nitric acid and organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, citric acid, benzoic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid and methanesulfonic acid.

The fact that at least one asymmetric carbon atom may be possible in the compounds of the formula I, for example in the dyhydrobenzofuranyl moeity of the group W₃ on carbon atom 2 or in the substituent R₆═OR₂₀, in which R₂₀ is a branched alkyl, alkenyl, haloalkyl or alkoxyalkyl group, or R₆═S(O)_(m)R₃₀, in which, for example, m=1 and/or R₃₀ is a branched alkyl, alkenyl, haloalkyl or alkoxyalkyl group, has the result that the compounds can occur not only in optically active individual isomers, but also in the form of racemic mixtures. In the present invention, the active ingredients of the formula I are to be understood as meaning not only the pure optical antipodes, but also the racemates or diastereomers.

If an aliphatic C═C— or C═N—O double bond (syn/anti) exists, geometric isomerism may occur. The present invention also embraces these isomers.

Preferred compounds of the formula I are those in which R₁ is methyl; and R₃ is methyl or ethyl.

Other preferred compounds of the formula I are those in which R₄ is fluorine.

Equally, preferred compounds of the formula I are those in which R₄ is chlorine.

Other preferred compounds of the formula I are those in which R₄ is hydrogen.

Important compounds of the formula I are those in which W is a group

(W₁), and R₄, R₅ and R₆ are as defined under formula I.

Especially preferred amongst these are the compounds in which R₅ is chlorine, bromine, methyl, cyano or trifluoromethyl.

Equally, important compounds of the formula I in which W is a group

(W₂); and R₄, R₆₀, R₆₁, X₁, X₂ and n₁ are as defined under formula I.

Especially important amongst these are, in particular, those in which R₄ is hydrogen, fluorine or chlorine; and X₁ is oxygen.

Other important compounds of the formula I are those in which W is a group

(W₃); R₄ is hydrogen, fluorine or chlorine and B₁ is methylene.

Important compounds are those of the formula I_(a)

in which W and R₁ to R₃ are as defined under formula I.

Especially important compounds are those of the formula I_(a.)

in which R, is methyl; R₂ is cyano; and R₃ is methyl or ethyl.

Very especially important compounds are those of the formula I_(a)

in which R₁ is methyl; R₂ is cyano; R₃ is methyl or ethyl; W is a group

(W₁); and R₄ is fluorine or chlorine.

Equally, very especially important compounds are those of the formula I_(a)

in which R₁ is methyl; R₂ is cyano; R₃ is methyl or ethyl; W is a group

(W₂); and R₄ is fluorine or chlorine.

Other very especially important compounds are those of the formula I_(a)

in which R₁ is methyl; R₂ is cyano; R₃ is methyl or ethyl; W is a group

(W₃); and R₄ is fluorine or chlorine.

The process according to the invention for the preparation of compounds of the formula I is carried out in analogy to known processes, for example as described in WO 96/01254, WO 97/00246 and EP-A-0 796 856 and comprises, to prepare those compounds of the formula I

in which W, R₁ and R₃ are as defined under formula I and R₂ is cyano,

a) dehydrating a compound of the formula IIa or IIb

in which W, R₁ and R₃ are as defined above; or

b) first diazotizing a compound of the formula IIIa or IIIb

in which W, R₁ and R₃ are as defined above and subsequently reacting the diazonium salt formed with a salt of the formula X

M⁺CN⁻  (X)

 in which M⁺ is an alkali metal, alkaline earth metal or transition metal ion; or

c) reacting a compound of the formula IVa or IVb

in which W, R₁ and R₃ are as defined above with hydroxylamine or a salt thereof, for example hydroxylamine·hydrochloride or hydrobromide or acetate, and dehydrating the oxime formed as an intermediate; or

d) reacting a compound of the formula Va or Vb

in which W, R₁ and R₃ are as defined under formula I and R₈₁, is C₁-C₄alkyl, C₃- or C₄alkenyl or benzyl with dimethylaluminium amide in the presence of an inert organic solvent.

The process according to the invention for the preparation of compounds of the formula I

in which W, R₁ and R₃ are as defined under formula I and R₂ is NH₂C(S)— is carried out in analogy to known processes and comprises

a) reacting a compound of this formula Ia or Ib

 with hydrogen sulfide in an organic solvent with base catalysis or with a hydrogen sulfide source with acid catalysis; or

b) reacting a compound of the formula IIa or IIb

in which W, R₁ and R₃ as defined above with a suitable sulfur reagent in a solvent.

The process according to the invention for the preparation of compounds of the formula Va and Vb

in which R₁ and W are as defined under formula I, R₃ is C₁-C₄alkyl, C₃- or C₄alkenyl or C₃- or C₄alkynyl; R₈₁ is C₁-C₄alkyl, C₃- or C₄alkenyl or benzyl comprises either

a) converting a compound of the formula XIa

in which W, R₁ and R₈₁ are as defined above with hydrazine to give the compound of the formula Vc

 and subsequently alkylating this compound in the presence of a compound of the formula XIIa

R₃—L₁  (XIIa)

 or of the formula XIIb

R₃OSO₂OR₃  (XIIb)

 the radical R₃ in the compounds of the formulae XIIa and XIIb being as defined above and L₁ being a leaving group; or

b) cyclizing a compound of the formula XIa

in which W, R₁ and R₈₁ are as defined above with the compound of the formula XIII

NH₂NH—R₃   (XIII)

 in which R₃ is as defined above.

The process according to the invention for the preparation of compounds of the formula VIa and VIb

in which R₁ and W are as defined under formula I and R₃ is C₁-C₄alkyl, C₃- or C₄alkenyl or C₃- or C₄alkynyl

comprises cyclizing a compound of the formula XIb

 in which W and R₁ are as defined above

a) with hydrazine to give the compound of the formula VIc

 and subsequently alkylating this compound in the presence of a compound of the formula XIIa

R₃—L₁  (XIIa)

 or of the formula XIIb

 R₃OSO₂OR₃  (XIIb)

the radical R₃ in the compounds of the formulae XIIa and XIIb being as defined above and L₁ being a leaving group; or

b) with a compound of the formula XIII

NH₂NH—R₃  (XIII)

 in which R₃ is as defined above.

The compounds of the formula I in which W is a group

A₁—B₁ is a group

R₄, R₇₀ and R₇₁ are as defined under formula I; and R₇₂ is C₁-C₆ alkyl can be obtained by reacting a compound of the formula VII

in which R₁ to R₄ and R₇₀ are as defined under formula I with a compound of the formula XIV

in which R₇₁ is as defined above; R₈ is hydrogen or C₁-C₅alkyl; and L₁ is a leaving group, in the presence or absence of an inert organic solvent and of a base, to give the compound of the formula VIIIa

in which R₁ to R₄, R₈, R₇₀ and R₇₁ are as defined above, subjecting this compound to a thermal or acid-catalyzed rearrangement reaction to give the compound of the formula IXa

 and subsequently cyclizing this compound.

The compound of the formula I in which W is a group

A₁—B₁ is a group

R₄, R₇₀ and R₇₁ are as defined under formula I; and R₇₂ is hydroxy-C₁-C₆alkyl can be obtained by epoxidizing a compound of the formula IXa

in which R₁ to R₄, R₇₀ and R₇₁ are as defined under formula I and R₈ is hydrogen or C₁-C₅alkyl and, if desired, subsequently cyclizing this compound in the presence of a catalyst.

The compounds of the formula I in which W is a group

A₁—B₁ is a group

R₄ and R₇₀ are as defined under formula I; and R₇₂ is C₁-C₆alkyl can be obtained by subjecting a compound of the formula VIIIb

in which R₁ to R₄ and R₇₀ are as defined under formula I and R₈ is hydrogen or C₁-C₅alkyl to a thermal rearrangement reaction to give the compound of formula IXb

 and subsequently cyclizing this compound.

The preparation of the compounds of the formula I is illustrated in greater detail in the reaction diagrams 1 to 7 which follow.

The radicals W, R₁ and R₃ in reaction diagram 1 are as defined under formula I, R₁ being in particular methyl or ethyl and R₈₁ being C₁-C₄alkyl, C₃- or C₄alkenyl or benzyl.

The ketone derivatives of the formula XX are reacted in accordance with reaction diagram 1 with a dialkyl oxalate of the formula XXI, preferably dimethyl oxalate, in the presence of a base, in particular the corresponding sodium alkoxide, preferably sodium methoxide, in a solvent, for example the corresponding alcohol, preferably methanol, together with a secondary solvent, for example an ether or hydrocarbon, at temperatures from 0°C. to the boiling point of the solvent in question. This condensation reaction and all subsequent reaction steps up to the nitrilo- and thioamidopyrazole derivatives of the formula I (Ia₁, Ib₁, Id and Ie) in accordance with reaction diagram 1 can be carried out in analogy to the procedure described in, for example, WO 96/01254 (page 20 et seq.).

According to this procedure, the diketo esters of the formula XIa are cyclized with a compound of the formula XIII, for example N-alkylhydrazine, at elevated temperature (reflux), preferably in glacial acetic acid, toluene or an alcohol as the solvent, to give the compounds of the formula V. If desired, an acid, for example sulfuric acid or p-toluenesulfonic acid may be employed as catalyst.

The subsequent conversion of the ester derivatives of the formula V into the corresponding amides of the formula II (Ila or llb) in accordance with reaction diagram 1 can be effected for example either directly by heating the ester derivatives in aqueous ammonia or, alternatively, via hydrolysis of the ester derivatives of the formula V to give the corresponding carboxylic acid derivatives of the formula Vi or Vj (R₁₃ ═OH) and subsequent heating of the resulting carboxylic acid derivatives in aqueous ammonia or via conversion of the carboxylic acid derivatives of the formula Vi or Vj (R₃═OH) into the corresponding carboxylic acid halides of the formula Vg or Vh (R₁₃═halogen, in particular chlorine) and subsequently heating the resulting carboxylic acid halides in aqueous ammonia.

The desired nitrolipyrazole derivatives of the formula I (Ia, or Ib₁; R₂═CN) can be obtained by dehydrating of the amides of the formula II (IIa or IIb) formed as above, for example in analogy to WO 96/01254, pages 23 and 41 et seq. and ‘Advanced Organic Chemistry’, Editor J. March, Mc Graw-Hill Book Company, N.Y., 1985, page 932 et seq.

The desired cyanopyrazole derivatives of the formula I (Id or Ie) (R₂═—C(S)NH₂) can be obtained

a) from the amides of the formula II (IIa or IIb) by means of sulfur reagents, for example Lawesson reagent, phosphorus pentasulfide or iron sulfide in various polar and unpolar solvents, for example toluene, xylenes, tetrahydrofuran, chloroform, dioxane or N,N-dimethylformamide, at temperatures from 20° C. to 150° C.; or

b) from the nitriles of the formula I (Ia₁ or Ib₁; R₂═CN) by means of a hydrogen sulfide source, for example hydrogen sulfide itself, with base catalysis.

The choice of the suitable preparation method and the corresponding reaction conditions depends on the properties (reactivities) of the substituents in the intermediates in question.

The preparation processes of the pyrazole rings are illustrated in greater detail in reaction diagrams 2, 3 and 4 which follow.

The pyrazole rings of the formulae Vc (reaction diagram 2, method a)) and XIXc (reaction diagram 3, method a)) are prepared by reacting the compounds of the formulae XIa, XId and XIe with hydrazine or hydrazine hydrate at elevated temperature.

To prepare the compound of the formula Vc, it is preferred to use glacial acetic acid or an alcohol as the solvent under mild reflux conditions, and for the preparation of the compound of the formula XIXc it is preferred to use toluene at elevated temperature. If desired, an acid, for example sulfuric acid or p-toluenesulfonic acid, may be employed as catalyst.

The pyrazole ring of the formula VIc, which is unsubstituted on the nitrogen atom (reaction diagram 4, method a), is preferably prepared from the compounds of the formula IXb in alcoholic solution with hydrazine hydrate at elevated temperature.

To prepare the pyrazole rings which are substituted on the nitrogen atom (reaction diagrams 2, 3 and 4, method b)) the procedure is as defined in analogy to method a), the reagent employed being the compound of the formula XIII, for example N-alkylhydrazine, preferably N-methylhydrazine.

The processes in accordance with method b) lead to isomer mixtures Va and Vb, XIXa and XIXb or VIa and VIb, the ratio of the two isomers depending, on the one hand, on the reaction conditions and, on the other hand, on the relevant intermediates of the formulae XIa, XId, XIe or XIb.

The mixtures of the isomeric pyrazole esters of the formulae Va and Vb can be readily separated into the pure isomers by means of silica gel chromatography and/or recrystallization. In general, the same also applies to the isomer mixtures of the formulae XIXa and XIXb, and VIa and VIb.

In certain cases, it is advantageous to prepare the N-alkyl-substituted pyrazole derivatives, in particular the N-methyl-substituted pyrazole derivatives, via N-alkylation of the corresponding unsubstituted pyrazoles of the formulae Vc, XIXc or VIc. This is illustrated in reaction diagram 5.

In reaction diagrams 2 to 5, the radical W is an aromatic system W₁ to W₃ as given under formula I; R₈₁ is C₁-C₄alkyl, C₃- or C₄alkenyl or benzyl; R₁ is C₁-C₄alkyl; R₃ is C₁-C₄alkyl, C₃- or C₄alkenyl or C₃- or C₄alkynyl; and L₁ is a leaving group, for example chlorine, bromine, iodine, CH₃SO₂O— or

The pyrazole rings in the compounds of the formulae Vc, XIXc, VIc, IVc and Ic in reaction diagram 5 are N-alkylated at room temperature or moderately elevated temperatures in the presence of a solvent, for example acetone, methyl ethyl ketone, N,N-dimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide, of a base, for example potassium carbonate, sodium carbonate, sodium hydroxide or potassium hydroxide, and of an alkylating agent of the formula XIIa or XIIb, preferably methyl iodide or dimethyl sulfate.

N-Alkylation of the pyrazole rings leads to isomer mixtures of the formulae Va and Vb, XIXa and XIXb, VIa and VIb, IVa and IVb, and Ia₁ and Ib₁ all of which can generally be separated into the pure isomers by customary processes.

The preparation of the pyrazole derivatives of the formula Ia₁—which are cyano-substituted in the 5-position—starting from the various intermediates of the formulae IIa, IIIa, IVa and Va, is illustrated in reaction diagram 6. The choice of the suitable preparation method and the relevant reaction conditions depends on the properties (reactivities) of the substituents in the intermediates in question.

In reaction diagram 6, the radicals W and R₁ are as defined under formula I, and R₃ ist C₁-C₄alkyl, C₃- or C₄alkenyl or C₃- or C₄alkynyl.

The reaction in accordance with method a) in reaction diagram 6 is effected in analogy to ‘Advanced Organic Chemistry’, Editor J. March, McGraw-Hill Book Company, N.Y., 1985, page 932 et seq. and converts primary amides of the formula IIa into the cyanopyrazoles of the formula Ia₁ with dehydration, for example using phosphorus pentoxide (P₂O₅), phosphorus oxychloride (POCl₃), acetic anhydride or trifluoroacetic anhydride, or carbon tetrachloride/triphenylphosphine (CCI₄/P(C₆H₅)₃), in the presence or absence of an inert solvent at elevated temperature.

The reaction in accordance with method b) in reaction diagram 6 is effected in analogy to ‘Vogel's Textbook of Practical Organic Chemistry’, 1989, page 938; according to this method, aminopyrazoles of the formula IIIa are first diazotized with sodium nitrite at low temperatures, for example −10° C. to 15° C., in aqueous hydrochloric acid and the diazonium salts formed are converted into the cyano derivatives of the formula Ia₁ with an aqueous solution of the salt of the formula X

M⁺CN⁻  (X)

in which M⁺ is an alkali metal ion, alkaline earth metal ion or transition metal ion, for example copper(l) cyanide or potassium cyanide (Sandmeyer reaction).

The reaction in accordance with method c) in reaction diagram 6 is effected in analogy to ‘Vogel's Textbook of Practical Organic Chemistry’, Longman 1989, page 1084, and allows pyrazolealdehydes of the formula IVa to react with hydroxylamine·hydrochloride in protic solvents to give oximes which are dehydrated in acetic anhydride at elevated temperature to give the cyanopyrazoles of the formula Ia₁.

In the reaction in accordance with method d) in reaction diagram 6, ester pyrazoles of the formula Va are used which can be converted directly into the nitrites of the formula Ia, in a mixture of inert solvents, preferably hexane, heptane, dichloromethane or xylene, and with heating to reflux temperature, with the aid of dimethylaluminium amide ((CH₃)₂AINH₂), which is freshly prepared from commercially available trimethylaluminium in accordance with known processes.

The reagents of the formulae X, XIIa, XIIb and XIII which are used in reaction diagrams 2 to 5 are known.

The pyrazolecarboxylic acids of the formula Vi

can be obtained in analogy to known processes

a) from the corresponding ester derivatives of the formula Va

 the radicals W, R₁ and R₃ in the compounds of the formulae Va and Vi being as defined under formula I and R₈₁ being C₁-C₄alkyl, C₃- or C₄alkenyl or benzyl, by means of hydrolysis, preferably with aqueous alcohols, aqueous tetrahydrofuran or aqueous N,N-dimethylformamide (DMF) in the presence of sodium hydroxide or potassium hydroxide at average temperatures, for example 0° C. to reflux temperature of the reaction mixture, followed by work-up under acidic conditions, or

b) by oxidation of an aldehyde of the formula IVa

for example with potassium permanganate.

The pyrazolecarboxylic acid chlorides of the formula Vg

can be prepared in analogy to known processes, for example ‘Organikum’ [Organic chemistry], Ed. J. A. Barth, Leipzig, 1993, page 439 et seq. from the corresponding pyrazolecarboxylic acids of the formula Vi

with inorganic acid chlorides, for example phosphorus trichloride or thionyl chloride, at elevated temperatures in the presence or absence of an inert solvent, the radicals W, R₁ and R₃ in the compounds of the formulae Vg and Vi being as defined above.

The pyrazolecarboxamides of the formula IIa

can be prepared in analogy to known processes

a) from the corresponding carboxylic acid chlorides of the formula Vg

 and aqueous ammonia solution at average temperatures, or

b) from certain ester derivatives of the formula Va

 in the presence of aqueous ammonia solution, the radicals W, R₁ and R₃ in formulae IIa, Vg and Va being as defined under formula I and R₈₁ being C₁-C₄alkyl, C3- or C₄alkenyl or benzyl, R₈₁ being in particular methyl.

In certain cases, for example when the nucleophilic character of the pyrazole ring is more pronounced than that of the phenyl ring, the aminopyrazoles of the formula IIIa

can be obtained by known processes, for example as described in Austr. J. Chem. 32,1727 (1979); J. Chem. Soc., Perkin Trans. 2,382 (1974); or J. Heterocycl. Chem. 20,277 (1983), from the compounds of the formula XIXa

by nitrating these compounds and subsequently reducing the nitro group; or in analogy to known processes, for example as described in J. Heterocycl. Chem. 19, 1173 (1982); Khim. Geterotsikl. Soedin 1990, 1092; Ber. Deutsch. Chem. Ges. 26, 2053 (1893); or Chem. Ber. 99, 1769 (1966), from compounds of the formula XXa

in which W and R₁ are as defined under formula I and compounds of the formula XIII

H₂NNH—R₃   (XIII)

 or a salt thereof, for example the corresponding hydrochloride or hydrobromide or acetate, preferably in a solvent, for example an alcohol or alcohol/water mixture or in acetic acid, at reaction temperatures of 20° C. to 100° C.

The pyrazolealdehydes of the formula IVa

can be prepared by known processes, for example as described in Arch. Pharm. 264, 337 (1926) and Liebigs Annalen 437, 297 (1924),

a) from the corresponding acid chlorides of the formula Vg

 or

b) from the corresponding acetals of the formula VIa

 by acid hydrolysis, for example with hydrochloric acid, sulfuric acid or p-toluene-sulfonic acid, the radicals W, R₁ and R₃ in the compounds of the formulae IVa, Vg and VIa, being as defined under formula I.

The preparation of the pyrazole thioamides of the formula Id starting from the corresponding pyrazolenitriles of the formula Ia₁ or pyrazole amides of the formula IIa is effected in analogy to known processes, for example as described in ‘Methodicum Chimicum’, Volume 6, Georg Thieme Verlag, Stuttgart, 1974, page 768 et seq. and ‘Methoden der Organischen Chemie’ [Methods in organic chemistry] (Houben-Weyl), Volume E5, Georg Thieme Verlag, Stuttgart, 1985, page 1242 et seq., and is illustrated in reaction diagram 7.

In reaction diagram 7 the radicals W, R₁ and R₃ in the compounds of the formulae Ia₁, IIa and Id are as defined under formula I, taking into consideration the reactivity or stability characteristics of the substituents under the reaction conditions chosen.

The reaction in accordance with method a), route a), in reaction diagram 7 uses pyrazolenitriles of the formula Ia₁ which can be converted into the pyrazole thioamides of the formula Id with hydrogen sulfide and base catalysis, for example with metal hydroxides, basic ion exchangers, alkoxides, ammonia or organic bases, for example pyridine and triethylamine, in an organic solvent, for example pyridine or an alcohol. If desired, the use of a stronger base, for example tetramethylguanidine, in solvents, for example sulfolane, as catalyst may be indicated. Depending on the reactivity of the reactants, the reaction temperatures can vary greatly; the reaction may also be carried out in a pressurized reactor if desired.

The reaction in accordance with method a), route b), in reaction diagram 7 also uses pyrazolenitriles of the formula Ia₁, which can be converted into the corresponding pyrazole thioamide of the formula Id with a hydrogen sulfide source, for example thioacetamide, in dry N,N-dimethylformamide with acid catalysis, for example with dry hydrogen chloride, at temperatures of from 20° C. to 150° C.

The reaction in accordance with method b) in reaction diagram 7 starts from primary amides of the formula IIa which, in the presence of the sulfur reagents mentioned under method a) or other sulfur reaagents, for example Lawesson reagent, phosphorus pentasulfide or iron sulfide, in a variety of polar and unpolar solvents, for example toluene, xylenes, tetrahydrofuran, chloroform, dioxane or N,N-dimethylformamide, and at temperatures of from 20° C. to 150° C. give the pyrazole thioamides of the formula Id.

All other compounds from amongst the scope of the formula I can be prepared in analogy to the procedure described above, or following methods as they are described, for example, in “Methoden der Organischen Chemie” [Methods in organic chemistry] (Houben-Weyl), Volume E 8b, Georg Thieme Verlag Stuttgart, 1994, page 399 et seq., in “Pyrazoles, Pyrazolines, Pyrazolidines, Indazoles and Condensed Rings”, Editor R. H. Wiley, lnterscience Publishers, New York, 1967, page 1 et seq., or in “Comprehensive Heterocyclic Chemistry”, Editors A. R. Katritzky and C. W. Rees, Pergamon Press, Oxford, 1987, or from the described compounds of the formula I by derivatization following known standard methods as they are described, for example, in “Advanced Organic Chemistry”, Third Edition, Editor J. March, John Wiley & Sons, New York, 1985; in “Comprehensive Organic Transformations”, Editor R. C. Larock, VCH Publishers, Inc., New York, 1989; or in “Comprehensive Organic Functional Group Transformations”, Editors A. R. Katritzky, O. Meth-Cohn, C. W. Rees, Pergamon Press, Oxford, 1995.

The starting compounds of the formula XX in reaction diagram 1 can be prepared in analogy to known processes, for example in accordance with methods a), b), c) and d) given in reaction diagram 8 below.

In reaction diagram 8, the radical W is a group W₁, W₂ or W₃, as defined under formula I, but it must be taken into consideration that not every definition of substituents is compatible with all the processes given. The choice of the suitable preparation method depends on the properties (reactivities) of the substituents in the intermediates in question.

The reaction in accordance with method a) in reaction diagram 8 is effected for example starting from the carboxylic acid of the formula XXIIa with alkyllithium of the formula XXIIIa or a Grignard compound of the formula XXIIIb (alkylmagnesium chloride or alkylmagnesium bromide) in an inert solvent, preferably diethyl ether, at temperatures of from −100° C. to 50° C., in analogy to Organic Reactions 18, 1 (1970), Organic Synthesis 49, 81 (1969) and ‘Comprehensive Organic Transformations’, Editor R. C. Larock, VCH 1989, page 685.

The reaction in accordance with method b) in reaction diagram 8 is effected in analogy to J. Chem. Soc. 1954, 1297. The amines of the formula XXIIb are first diazotized to give the corresponding diazonium salts and these are reacted with the oxime of the formula XXIV. Subsequent hydrolysis, for example with aqueous sodium acetate and copper sulfate, gives the corresponding methyl ketone of the formula XX.

The reaction in accordance with method c) in reaction diagram 8 is effected in analogy to ‘Vogel's Textbook of Practical Organic Chemistry’, Longman 1989, page 1006 et seq. Here, the aromatic compound of the formula XXII is reacted in the presence of an alkanecarboxylic acid derivative of the formula XXV for example propionyl chloride, and an acid, for example Lewis acids such as aluminium chloride, with or without solvent at temperatures of from 0° C. to 150° C.

The reaction in accordance with method d) in reaction diagram 8 is effected in analogy to ‘Advanced Organic Chemistry’, Editor J. March, McGraw-Hill Book Company, New York, 1985, pages 816 et seq. and 1057 et seq., starting from an aldehyde of the formula XXIIc, by means of a Grignard reagent of the formula XXIIIb for example ethylmagnesium chloride or ethyl magnesium bromide, or by means of ethyllithium in an inert solvent, preferably diethyl ether, at temperatures of from −80° C. to 25° C. and subsequent oxidation of the alcohol to give the ketone. Suitable oxidants are, for example, potassium permanganate, pyridinium dichromate and sodium dichromate.

The starting compounds of the formulae XXII, XXIIa, XXIIb and XXIIc are known and can be prepared by processes which have been disclosed.

The starting compounds of the formula XXa can be prepared in analogy to standard processes, for example

a) via Reformatsky reaction of a bromonitrile of the formula XV

 in which R₁ is as defined under formula I with a nitrile of the formula XXIId

W—CN  (XXIId)

 in which W is as defined under formula I and subsequent hydrolysis in analogy to the procedure described in, for example, Organomet. Chem. 71, 325 (1974); or

b) via condensation of a nitrile of the formula XVI

R₁—CH₂—CN  (XVI)

 in which R₁ is as defined under formula I with an ester of the formula XXIIe

W—COOR₇  (XXIIe)

 in which W is as defined above and R₇ is methyl or ethyl in the presence of a base, for example an alkoxide, for example sodium methoxide or sodium ethoxide, in a solvent, for example methanol or ethanol, in analogy to the procedure described in, for example, J. Am. Chem. Soc. 54, 2960 (1932); ibid. 79, 723 (1957); or in Tetrahedron Lett. 1979, 1585; or

c) via substitution of the compound of the formula XXb

 in which W and R₁ are as defined above and L₁ is a leaving group, for example chlorine or bromine, in analogy to the procedure described in, for example, J. Heterocycl. Chem. 21, 1849 (1984); or

d) via alkylation of a ketonitrile of the formula XXc

 with an alkylating agent of the formula XIIc

R₁—L₁  (XIIc),

 W and R₁ in the compounds of the formulae XXc and XIIc being as defined above and L₁ being a leaving group, for example, chlorine, bromine or C₆H₅SO₂O—, in the presence of a base and of a solvent in analogy to the procedure described in, for example, J. Am. Chem. Soc. 61, 1940 (1939).

The intermediates of the formulae XIa, XIb, XId and XIe in reaction diagrams 2 to 4 can be prepared in analogy to known processes from the above-described methyl ketones of the formula XX, for example in accordance with methods a), b), c) and d) given in reaction diagram 9 below.

The radicals W and R₁ in reaction diagram 9 are as defined under formula I, and R₈₁ is C₁-C₄alkyl, C₃- or C₄alkenyl or benzyl, in particular methyl or ethyl.

The reaction in accordance with method a) in reaction diagram 9 gives the diketo esters of the formula XIa, either by reacting route a) the ketone of the formula XX with a dialkyl oxalate of the formula XXI, preferably dimethyl malonate, in the presence of a base, in particular the corresponding sodium alkoxide, in a solvent, for example the corresponding alcohol R₈₁OH, together with a secondary solvent, for example an ether or hydrocarbon, at temperatures of from 0° C. to the boiling point of the solvent in question, in analogy to Chem. Communic. 1995, 1549; Liebigs Ann. 641, 63 (1961); and J. Chem. Soc. 1943, 491, or route b) the ketone of the formula XX with a hexaalkoxyethane of the formula XXIa, preferably hexamethoxy- or hexaethoxyethane, with or without solvent, at temperatures of from 20° C. to the boiling point of the reaction medium in question. If the reaction is carried out in a solvent, then toluene is preferred. The reaction can be catalyzed by acids, for example hydrochloric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid or trifluoroacetic acid.

The reactions in accordance with methods c) and d) in reaction diagram 9 proceed in analogy to the procedure described under a) and give the intermediates of the formulae XId and XIe. If the ketone of the formula XX is reacted, on the one hand, with acetals of N,N-dimethylformamide of the formula, XXVIb, preferably N,N-dimethylformamide dimethyl acetal or N,N-dimethylformamide diethyl acetal, the intermediates of the formula XId are formed, or, on the other hand, with orthoformates of the formula XXVII, preferably methyl orthoformate or ethyl orthoformate, the intermediates of the formula XIe are formed.

The reaction of the ketone of the formula XX in accordance with method b) in reaction diagram 9 with acetal esters of the formula XXVIa, preferably methyl dimethoxyacetate or ethyl diethoxy acetate, in the presence of a base, preferably sodium methoxide or sodium ethoxide, and of a solvent, in particular methanol or ethanol, at temperatures of from 0° C. to the boiling point of the reaction mixture gives the diketo acetals of the formula XIb. In certain cases, a further solvent, for example ether, can also be added.

To prepare the phenylpyrazoles of the formula I which are substituted in the 5-position of the phenyl ring (group W₁, substituent R₆), a large number of known standard processes is available, the choice of the suitable preparation processes depending on the properties (reactivities) of the substituents in the intermediates in question. Some illustrative examples are given in reaction diagrams 10 to 13.

The preparation of the phenylpyrazole derivatives of the formula I (W=W₁) which are O-substituted in the 5-position of the phenyl ring, and in which R₆=OR₂₀, starting from the methoxy- or benzyloxy-substituted derivatives of the formula I₃₇ or I₃₈ is illustrated in reaction diagram 10.

The phenylpyrazole derivatives of the formula I₃₉ in reaction diagram 10 can be obtained for example a) from the compounds of the formula I₃₇ via ether cleavage by means of lithium chloride in N,N-dimethylformamide (DMF) at elevated temperature, for example as described in Synthesis 1989, 287, or by means of boron tribromide in dichloromethane at temperatures of from −80° C. to 20° C., for example as described in Org. Synth., Collect. Vol. V, 412, 1973; or b) from the compound of the formula I₃₈ via hydrogenolysis by means of hydrogen in the presence of a catalyst, for example palladium on charcoal, for example as described in J. Am. Chem. Soc. 93, 746 (1971). Derivatization of the phenylpyrazole of the formula I₃₉ in reaction diagram 10 to give the compounds of the formula I can be carried out by standard processes, for example via alkylation with R₂₀-hal, in which R₂₀ is as defined under formula I and hal is halogen, in particular chlorine, bromine or iodine.

The preparation of the phenylpyrazole derivatives of the formula I (W=W₁) which are S-substituted in the 5-position of the phenyl ring, and in which R₆=S(O)_(m)R₃₀, starting from the derivatives of the formula I₄₀ which are unsubstituted in the 5-position is illustrated in reaction diagram 11.

The preparation of the thiophenylpyrazoles of the formula I₄₂ in reaction diagram 11 can be effected in analogy to known processes, for example as described in J. Org. Chem. 54, 6096 (1989), EP-A-0 259 265 or in “Sulfonation and Related Reactions”, Editor Gilbert, lnterscience Publishers, New York, 1965. Thereafter, the phenylpyrazole of the formula I₄₀ can be chlorosulfonylated with chlorosulfonic acid or sulfur trioxide in sulfuric acid to give the compound of the formula I₄₁ and this is subsequently reduced with tin chloride or zinc chloride to give the thiophenol derivative of the formula I₄₂. Derivatization of the thiophenylpyrazoles of the formula I₄₂ to give the compounds of the formula I in reaction diagram 11 can be effected by standard processes, for example via alkylation with R₃₀-hal, in which R₃₀ is as defined under formula I and hal is halogen, in particular chlorine, bromine or iodine (m=0). The subsequent oxidation to give the sulfone or sulfone derivatives of the formula I (m=1 or 2, respectively) can equally be carried out by standard processes, for example with peracids, for example m-chloroperbenzoic acid.

The preparation of the phenylpyrazole derivatives of the formula I (W=W₁) which are carboxyl-substituted in the 5-position of the phenyl ring, and in which R₆=halogen, cyano, nitro, amino, R₁₀NH or R₁₀R₁₁N, starting from the derivatives of the formulae I₄₀ and I₄₇ which are unsubstituted or triflate-substituted in the 5-position, respectively, is illustrated in reaction diagram 12.

In reaction diagram 12, Q is the radical

in which R₁ to R₃ are as defined under formula I.

In accordance with reaction diagram 12, the phenylpyrazole of the formula I₄₀ can be converted into the aniline derivative of the formula I₄₄ by standard processes, for example nitration in a mixture of nitric and sulfuric acid and subsequent reduction of the resulting nitro compound of the formula I₄₃ with hydrogen in the presence of a catalyst, or by the method of Bechamps. Then, the aniline derivative of the formula I₄₄ can either be derivatized directly by standard processes, for example acylation or ethylation, to give the corresponding compounds of the formula I or converted into the halogen compound of the formula I₄₅ by means of diazotization and Sandmeyer reaction. The benzoate of the formula I₄₆ in reaction diagram 12 can be obtained for example in analogy to J. Org. Chem. 39, 3318 (1974) or ibid. 40, 532 (1975) from the compound of the formula I₄₅ by means of carbon monoxide and a catalyst, for example palladium chloride triphenylphosphine (PdCI₂(TPP)₂) in the presence of a solvent, for example ethanol, at elevated temperature, with or without pressure. A further possibility of synthesizing the intermediate of the formula I₄₆ is in analogy to Tetrahedron Letters 25, 2271 (1984) and ibid. 27, 3931 (1986). In accordance with this, the compound of the formula I₄₇ is carbonylated in the presence of a catalyst, for example palladium. Subsequent hydrolysis of the benzoate ester of the formula I₄₆ gives the benzoic derivative of the formula I₄₈, which can be converted into the corresponding compounds of the formula I by standard processes, for example esterification or amidation.

The preparation of the phenylpyrazole derivatives of the formula I (W=W₁) which are substituted in the 5-position of the phenyl ring and in which R₆ R₅₂ZC(O)—C₁-C₈alkyl, R₅₂ZC(O)—C₁-C₈haloalkyl, R₅₂ZC(O)—C₂-C₈alkenyl, R₅₂ZC(O)—C₂-C₈alkynyl, R₅₂ZC(O)—C₂-C₈haloalkenyl, R₅₂ZC(O)—C₁-C₄alkoxy-C₁-C₄alkyl or R₅₂ZC(O)—C₁-C₄alkylthio-C₁-C₄alkyl, starting from the derivatives of the formula I₄₅ which are substituted in the 5-position of the phenyl ring by halogen, in particular chlorine, bromine or iodine, via a Heck reaction (route a)) or starting from the derivatives of the formula I₄₄ which are amino-substituted in the 5-position of the phenyl ring via diazotization and subsequent Meerwein reaction (route b)) is illustrated in reaction diagram 13.

In reaction diagram 13, Q is the radical

in which R₁ to R₃ are as defined under formula I.

In accordance with reaction diagram 13, route a), the alkynyl ester derivatives of the formula I₄₉ can be prepared for example via a Heck reaction in analogy to R. F. Heck in W. G. Dauben (Edit.), Organic Reactions 27, 345 (1982). The corresponding R₅₂ZC(O)alkenyl or R₅₂ZC(O)alkyl derivatives can be obtained via standard processes, for example by means of partial or complete hydrogenation, and the corresponding R₅₂ZC(O)haloalkenyl or R₅₂ZC(O) haloalkyl derivatives of the formula I via halogenation.

In accordance with reaction diagram 13, route b), the R₅₂ZC(O)haloalkyl derivatives of the formula I₅₀ can be prepared from the aniline derivatives of the formula I₄₄ in analogy to Organic Reactions 11, 189-260 (1960) via diazotization and Meerwein reaction. The corresponding R₅₂ZC(O)alkyl or R₅₂ZC(O)alkenyl derivatives of the formula I are obtained therefrom by known standard processes, for example hydrogenolysis or elimination of halogen.

The preparation of the benzofuran and dihydrobenzofuran rings of the compounds of the formula I in which W is a group

(W₃) and R₄, R₇₀ and A₁-B₁ are as defined under formula I is illustrated in greater detail in reaction diagrams 14, 15 and 16 which follow.

In reaction diagrams 14,15 and 16, Q is the radical

in which R₁ to R₃ are as defined under formula I.

The allyl ethers of the formula VIIIa can be obtained in accordance with reaction diagram 14, for example in analogy to EP-A-0 617 033 (page 3, lines 45 and 46) or U.S. Pat. No. 4,881,967 (column 11, lines 17-39) by means of reacting the compounds of the formula VII with an allyl derivative of the formula XIV, in which L₁ is a leaving group, e.g. halogen, in particular chlorine or bromine, with or without an inert organic solvent, for example acetone, acetonitrile or N,N-dimethylformamide, in the presence of a base, for example potassium carbonate.

The allylated phenol derivatives of the formula IXa are obtained by subjecting the corresponding allyl ethers of the formula VIIIa to a thermal rearrangement reaction. This rearrangement reaction (Claisen rearrangement) is effected for example in analogy to EP-A-0 617 033 (page 3, lines 17-44) or U.S. Pat. No. 4,881,967 (column 10, line 30 to end of column 10), with or without a solvent, for example toluene, xylenes, mesitylene or tetralin and tertiary amines, for example N,N-diethylaniline or mixtures thereof, at temperatures of from 20° to 300° C., preferably at from 100° C. to 250° C., for 0.5 to 48 hours. If desired, the rearrangement reaction may be carried out in a sealed pressurized container.

Alternatively, this rearrangement reaction may also be carried out in the presence of a Lewis acid catalyst, for example boron trichloride, in an inert solvent, for example dichloromethane, at temperatures of from 0° C. to 25° C., for example in analogy to U.S. Pat No. 4,881,967 (column 10, line 66 to end of column 10, and column 11, lines 1-7).

The subsequent cyclization reaction of the compounds of the formula IXa can be carried out by one or more methods, for example as described in U.S. Pat. No. 4,881,967 (column 8, lines 56 to end of column 8, and column 9, lines 1-3), but in particular with acid catalysis in an inert organic solvent, for example xylenes, in the presence of acids, for example p-toluene-sulfonic acid.

The preparation of the compounds of the formula I in which R₇₂ is hydroxy-C₁-C₆alkyl (R₇₂=—CH(OH)—R₈) is effected in accordance with reaction diagram 15 by epoxidizing the compound of the formula IXa, for example with m-chloroperbenzoic acid (MCPA), in the presence of an organic solvent and subsequently cyclizing the product in analogy to, for example, EP-A-0 617 033 (page 3, last section, and page 4, lines 1-50).

The allyl ethers of the formula VIIIb in reaction diagram 16 can be obtained for example in analogy to EP-A-0 561 319 from the corresponding phenols of the formula VII and the allyl derivatives of the formula XIV (reaction diagram 14; R₇₁=chlorine). The phenols of the formula IXb can be obtained by heating the allyl ethers of the formula VIIIb, in analogy to the procedure described in reaction diagram 14. This thermal rearrangement reaction is effected at temperatures of from 150° C. to 250° C. over 2 to 100 hours with or without an inert organic solvent.

Subsequent cyclization of the phenols of the formula IXb is expediently effected in the presence of an acid, e.g. mineral acids, for example hydrochloric acid, sulfuric acid or polyphosphoric acid, organic acids, for example p-toluenesulfonic acid or trifluoromethanesulfonic acid and carboxylic acids, for example formic acid, acetic acid or trifluoroacetic acid. The amount of acid used relative to phenols of the formula Vb is 1.1:1 up to 100:1.

The cyclization reaction is effected with or without a solvent, e.g. aromatic hydrocarbons, for example benzene or toluene, halogenated hydrocarbons, for example chloroform or carbon tetrachloride, mineral acids, for example hydrochloric acid or sulfuric acid, organic acids, for example acetic acid, and water. These solvents can also be employed in the form of a mixture.

This cyclization is successfully carried out at temperatures of from 0° C. to 100° C., preferably at from 5° C. to 80° C., over 0.5 to 24 hours.

All further functionalization reactions of the substituent R₇₂ (or —CH₂R₈ or —CH(OH)—R₈) in the 2-position of the benzofuranyl or dihydrobenzofuranyl increment to give the compounds of the formula I can be effected starting from the compounds of the formulae I in reaction diagrams 14, 15 and 16 in analogy to the procedure described in, for example, EP-A-0 617 033 (page 3, last section, up to page 8), EP-A-0 561 319 (page 3, last section, up to page 10) or U.S. Pat. No. 4,881,967 (columns 13 and 14).

The starting phenols of the formula VII (reaction diagram 14) can be obtained for example as shown in reaction diagram 17 from the corresponding methoxy- or benzyloxy-substituted derivatives of the formula VII₁ or VII₂, respectively, in which R₄and R₇₀ are as defined under formula I and Q is the radical

in which R₁ to R₃ are as defined under formula I.

In accordance with this diagram, route a), the compounds of the formula VII₁ are subjected to ether cleavage by means of lithium chloride in N,N-dimethylformamide (DMF) at elevated temperature, for example as described in Synthesis 1989, 287, or by means of boron tribromide in dichloromethane at temperatures of from −80° C. to 20° C., as described, for example, in Org. Synth., Collect. Vol. V, 412, 1973, or, in accordance with route b), the compounds of the formula VII₂ are subjected to hydrogenolysis by means of hydrogen in the presence of a catalyst, for example palladium on charcoal, as described, for example, in J. Am. Chem. Soc. 93, 746 (1971).

The compounds of the formula VII₁ and VII₂ in reaction diagram 17 can be prepared by standard methods, for example as described in U.S. Pat. No. 4,452,981 and EP-A-0 061 741, from the known phenols of the formula VII₃

in which R₄ and R₇₀ are as defined under formula I by means of nitrating the benzene ring and methylating or benzylating, respectively, the phenol function and subsequently reducing the nitro group to give the corresponding aniline derivative of the formula VII₄

in which R₄ and R₇₀ have the abovementioned meanings and R₁₂ is methyl or benzyl and subsequently constructing the pyrazole ring as described above.

The starting compounds of the formula XIV in reaction diagram 14 are known or can be prepared by disclosed processes.

A large number of known standard processes is available for the preparation of all other compounds of the formula I (W=W₃; R₇₂) which are substituted in the 2-position of the benzofuranyl or dihydrobenzofuranyl ring, for example alkylation, halogenation, acylation, amidation, oximation, oxidation and reduction, the choice of the suitable preparation process depending on the properties (reactivities) of the substituents in the intermediates in question.

The intermediates of the formula V₀

in which R₁, R₃ and W are as defined under formula I and R₀₂ is HOC(O)—, OHC—, C₁-C₄alkoxycarbonyl, C₃— or C₄alkenyloxycarbonyl, benzyloxycarbonyl, (C₁-C₄alkoxy)₂CH—, (C₁-C₄alkyl)-O—N═CH—, (C₁-C₄alkylsolfonyl)-O—N═CH—, (C₁-C₄haloalkylsulfonyl)-O—N═CH—, (C₁-C₄alkoxycarbonyl)-O—N═CH—, (C₁-C₄haloalkoxycarbonyl)-O—N═CH—, amino, CIC(O)— or H₂NC(O)— are novel. They represent important intermediates for the synthesis of the compounds of the formula I. The invention thus also relates to these compounds, with the exception of the compounds of the formulae

The end products of the formula I can be isolated in the customary manner by concentrating or evaporating the solvent and purified by recrystallization or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons, by distillation or by means of column chromatography and a suitable eluent.

Those skilled in the art will furthermore know in which sequence certain reactions, for example in reaction diagrams 1, 12 and 14, are to be carried out expediently to avoid secondary reactions which may occur.

Unless a target-orientated synthesis is carried out for isolating pure isomers, the product may be obtained in the form of a mixture of two or more isomers. The isomers can be separated by methods known per se.

Suitable application methods for the use according to the invention of the compounds of the formula I or compositions comprising them are all those which are conventionally used in agriculture, for example pre-emergence application, post-emergence application and seed dressing, and also various methods and techniques, for example the controlled release of active ingredient. To this end, the dissolved active ingredient is applied to mineral carriers for granules or polymerized granules (urea/formaldehyde) and dried. If desired, a coating can additionally be applied (coated granules) which allows controlled release of the active ingredient over a specific period.

The compounds of the formula I can be employed in unaltered form, i.e. as obtained in synthesis, but they are preferably processed in the customary manner together with the auxiliaries conventionally used in the art of formulation, for example to give emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. The application methods, such as spraying, atomizing, dusting, wetting, spreading or pouring and also the type of the compositions are chosen to suit the intended aims and the prevailing circumstances.

The formulations, i.e. the compositions, preparations or products comprising the active ingredient of the formula I or at least one active ingredient of the formula I and, as a rule, one or more solid or liquid formulation auxiliaries, are prepared in the known manner, for example by intimately mixing and/or grinding the active ingredients with the formulation auxiliaries, for example solvents or solid carriers. Furthermore, surface-active compounds (surfactants) may additionally be used when preparing the formulations.

Suitable solvents can be: aromatic hydrocarbons, preferably the fractions C₈ to C₁₂, for example xylene mixtures or substituted naphthalenes, phthalic esters such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols, and their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or N,N-dimethylformamide, and epoxidized or unepoxidized vegetable oils, such as epoxidized coconut oil or soya oil, or water.

Solid carriers which are used for example for dusts and dispersible powders are, as a rule, ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties of the formulation, it is also possible to add highly disperse silica or highly disperse absorptive polymers. Possible particulate, adsorptive carriers for granules are porous types, for example pumice, brick grit, sepiolite or bentonite, and suitable non-sorptive carrier materials are, for example, calcite or sand. In addition, a large number of pregranular materials of inorganic or organic nature, such as, in particular dolomite or comminuted plant residues, may be used.

Suitable surface-active compounds are, depending on the type of the active ingredient of the formula I to be formulated, non-ionic, cationic and/or anionic surfactants and surfactant mixtures which have good emulsifying, dispersing and wetting properties.

Suitable anionic surfactants can be not only so-called water-soluble soaps, but also water-soluble synthetic surface-active compounds.

Soaps which may be mentioned are the alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts of higher fatty acids (C₁₀-C₂₂), for example the sodium or potassium salts of oleic or stearic acid or of natural fatty acid mixtures which can be obtained, for example, from coconut or tallow oil. Mention must also be made of the fatty acid methyltaurinates.

However, so-called synthetic surfactants are used more frequently, in particular fatty alcohol sulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

As a rule, the fatty alcohol sulfonates or fatty alcohol sulfates are present in the form of alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts and have an alkyl radical of 8 to 22 C atoms, alkyl also including the alkyl moiety of acyl radicals, for example the sodium or calcium salt of lignosulfonic acid, of the dodecylsulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. This section also includes the salts of the sulfuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfo groups and one fatty acid radical of 8-22 C atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid of dibutylnaphthalene-sulfonic acid or of a naphthalenesulfonic acid/formaldehyde condensate.

Other possible substances are suitable phosphates, for example salts of the phosphoric ester of a p-nonylphenol, (4-14)ethyleneoxide adduct, or phospholipids.

Suitable non-ionic surfactants are mainly polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.

Other suitable non-ionic surfactants are the water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol which have 1 to 10 carbon atoms in the alkyl chain and contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. The abovementioned compounds normally contain 1 to 5 ethylene glycol units per polypropylene glycol unit.

Examples which may be mentioned of non-ionic surfactants are nonylphenylpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Also suitable are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

The cationic surfactants are, in particular, quaternary ammonium salts which contain, as N-substituents, at least one alkyl radical of 8 to 22 C atoms and as further substituents lower halogenated or unhalogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, for example stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants conventionally used in the art of formulation, which may also be used in the compositions according to the invention, are described, inter alia, in “Mc Cutcheon's Detergents and Emulsifiers Annual” MC Publishing Corp., Ridgewood N.J., 1981, Stache, H., “Tensid-Taschenbuch” [Surfactant Guide], Carl Hanser Verlag, Munich/Vienna, 1981, and M. and J. Ash, “Encyclopedia of Surfactants”, Vol I-III, Chemical Publishing Co., New York, 1980-81.

The herbicidal formulations comprise, as a rule, 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of herbicide, 1 to 99.9% by weight, in particular 5 to 99.8% by weight, of a solid or liquid formulation auxiliary and 0 to 25% by weight, in particular 0.1 to 25% by weight, of a surfactant.

While concentrated compositions are more preferred as commercially available goods, the end user uses, as a rule, dilute compositions.

The compositions can also comprise other additives such as stabilizers, for example epoxidized or unepoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soya oil), antifoams for example silicone oil, preservatives, viscosity regulators, binders, tackifiers and fertilizers or other active ingredients.

Preferred formulations are composed in particular as follows:

(%=per cent by weight)

Emulsifiable concentrates: Active ingredient: 1 to 90%, preferably 5 to 50% Surfactant: 5 to 30%, preferably 10 to 20% Solvent: 15 to 94%, preferably 70 to 85% Dusts: Active ingredient: 0.1 to 50%, preferably 0.1 to 1% Solid carrier: 99.9 to 90%, preferably 99.9 to 99% Suspension concentrates: Active ingredient: 5 to 75%, preferably 10 to 50% Water: 94 to 24%, preferably 88 to 30% Surfactant: 1 to 40%, preferably 2 to 30% Wettable powders: Active ingredient: 0.5 to 90%, preferably 1 to 80% Surfactant: 0.5 to 20%, preferably 1 to 15% Solid carrier: 5 to 95%, preferably 15 to 90% Granules: Active ingredient: 0.1 to 30%, preferably 0.1 to 15% Solid carrier: 99.5 to 70%, preferably 97 to 85%

As a rule, the active ingredients of the formula I can be applied successfully to the plant or its environment at rates of application of 0.001 to 4 kg/ha, in particular 0.005 to 2 kg/ha, either as a mixture composed of the isomers Ia and Ib or as pure isomers Ia or Ib. The dosage required for the desired action can be determined by experiments. It depends on the type of action, the developmental stage of the crop plant and of the weed and on the application (location, timing, method) and it can vary within wide ranges due to these parameters.

The compounds of the formula I and, as a rule, especially the isomers of the formula Ia are distinguished by herbicidal and growth-inhibiting properties which make them suitable for use in crops of useful plants, in particular in cereals, cotton, soya, sugar beet, sugar cane, plantations, oilseed rape, maize and rice, and for non-selective weed control (‘total vegetation mangement’, TVM).

Crops are also to be understood as including those which have been made tolerant to herbicides or classes of herbicides by conventional plant-breeding or genetic engineering methods. The weeds to be controlled can be not only monocotyledoneous, but also dicotyledoneous weeds, for example Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Phaseolus, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.

The examples which follow illustrate the invention in greater detail without imposing any limitation.

Preparation Examples EXAMPLE H1 3-(4-chloro-2-fluoro-5-methoxyphenyl)-4-methyl-5-methoxycarbonyl-[1H]-pyrazole

13.0 g of 1-(4-chloro-2-fluoro-5-methoxyphenyl)-1-propanone and 7.4 g of dimethyl oxalate are introduced into 50 ml of absolute tetrahydrofuran. 12 ml of a 5.4-molar solution of sodium methoxide in methanol are added dropwise with stirring at 22° C. in the course of 10 minutes, and stirring is subsequently continued for 1 hour. Thin-layer analysis (silica gel 60 F₂₅₄, n-hexane/ethyl acetate/glacial acetic acid=20/20/1 (v/v/v), UV) of a worked-up sample shows that all of the starting material has reacted.

The reaction mixture is poured into a mixture of ice and 2-molar hydrochloric acid and extracted with diethyl ether. The ether phase is washed with water and saline, dried over sodium sulfate, filtered and concentrated in vacuo. This gives 18.0 9 of a yellow solid which is introduced into 80 ml of glacial acetic acid. Thereupon, 3.2 ml of hydrazine hydrate are added slowly, using a syringe (exothermic). The mixture is subsequently refluxed gently overnight with stirring. The reaction mixture is evaporated to dryness in vacuo, and the residue is diluted with carbon tetrachloride and reconcentrated. The residue obtained is applied to 40 g of silica gel from ethyl acetate. After the silica gel had been applied to a flash chromatography column, it is eluted with a mixture of n-hexane/ethyl acetate/glacial acetic acid=100/50/1 (v/v/v). This gives 3.2 g of the desired compound as a yellow solid. Mass spectrum: [M⁺]298, 266, 210.

EXAMPLE H2 3-(4-chloro-2-fluoro-5-methoxyphenyl)-4-methyl-5-methoxycarbonyl-1-methyl-[1H]-pyrazole

4.0 g of 3-(4-chloro-2-fluoro-5-methoxyphenyl)-4-methyl-5-methoxycarbonyl-[1H]-pyrazole (Example H1) are dissolved in 15 ml of dry N-methylpyrrolidone. After 5.6 g of potassium carbonate have been added, the mixture is stirred, a solution of 2.1 g of methyl iodide in 2 mI of N-methylpyrrolidone is slowly added dropwise at 22° C., and stirring is continued for 4 hours at the same temperature. Thin layer analysis (silica gel 60 F₂₅₄, toluene/glacial acetic acid 10/1 (v/v), UV) of a worked-up sample shows that starting material is no longer present. The reaction mixture is diluted with water and extracted with diethyl ether. The combined organic phases are washed with water, dried over sodium sulfate and filtered, and the filtrate together with 8 g of silica gel is evaporated to dryness in vacuo. After the silica gel has been applied to a flash chromatography column, it is eluted with a mixture of n-hexane/ethyl acetate=2/1 (v/v). This gives 2.6 g of the desired compound of m.p. 135-137° C.

1.35 g of the regioisomeric 5-(4-chloro-2-fluoro-5-methoxyphenyl)-4-methyl-3-methoxycarbonyl-1-methyl-[1H]-pyrazole of m.p. 99-1 03° C. are eluted in the next fraction as byproduct.

EXAMPLE H3 3-(4-chloro-2-fluoro-5-methoxyphenyl)-4-methyl-5-carboxyl-1-methyl-[1H]-pyrazole

2.3 g of 3-(4-chloro-2-fluoro-5-methoxyphenyl)-4-methyl-5-methoxycarbonyl-1-methyl-[1H]-pyrazole (Example H2) are introduced at 22° C. into 20 ml of dioxane, and 4 ml of a 3-molar aqueous sodium hydroxide solution is then added dropwise. The reaction solution is then stirred overnight and subsequently acidified with dilute hydrochloric acid and extracted with ethyl acetate. The combined organic phases are washed with water and saline, dried over sodium sulfate and filtered, and the filtrate is evaporated to dryness in vacuo. This gives 2.2 g of the desired compound as white solid.

¹H NMR: (DMSO-D₆): acid proton in offset; 7.55 ppm (1H, d); 7.11 ppm (1H, d); 4.10 ppm (3H, s); 3.86 ppm (3H, s).

EXAMPLE H4 3-(4-chloro-2-fluoro-5-methoxyphenyl)-4-methyl-5-carbamoyl-1-methyl-[1H]-pyrazole

2,2 g of 3-(4-chloro-2-fluoro-5-methoxyphenyl)-4-methyl-5-carboxyl-1-methyl-[1H]-pyrazole (Example H3) are introduced into 10 ml of 1,3-dichloroethane. First, a few drops of dimethylformamide and then 1.3 ml of thionyl chloride are added. The suspension is refluxed gently overnight, with stirring. The yellow solution is subsequently evaporated in vacuo, treated with 20 ml of carbon tetrachloride and reconcentrated. This gives 2.48 g of a yellow solid which is dissolved in 3 ml of tetrahydrofuran. This solution is added dropwise at 22° C. to 20 ml of a 30% aqueous ammonia solution, and stirring is continued for 2 hours. The resulting suspension is extracted with ethyl acetate, and the combined organic phases are washed with water and saline, dried over sodium sulfate, filtered and evaporated to dryness in vacuo. This gives 2.0 g of the desired compound as a pale brown solid of m.p. 224-226° C.

EXAMPLE H5 3-(4-chloro-2-fluoro-5-methoxyphenyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole

2.0 g of 3-(4-chloro-2-fluoro-5-methoxyphenyl)-4-methyl-5-carbamoyl-1-methyl-[1H]-pyrazole (Example H4) are introduced into 10 ml of dioxane. After 1.3 ml of pyridine have been added, the mixture is cooled in an ice-bath, and 1.4 ml of trifluoroacetic anhydride are added dropwise using a syringe, with stirring. Stirring is continued for 1hour with cooling. Thin-layer analysis (silica gel 60 F₂₅₄, n-hexane/ethyl acetate 1/1 (v/v), UV) of a worked-up sample shows that all of the starting material has been reacted. The reaction mixture is diluted with ethyl acetate and extracted in succession with dilute hydrochloric acid, dilute sodium bicarbonate solution and saline. The organic phase is dried over sodium sulfate and filtered, and the filtrate is evaporated to dryness in vacuo. This gives 1.8 g of the desired product as a colourless solid of m.p. 155-156° C.

The regioisomeric 5-(4-chloro-2-fluoro-5-methoxyphenyl)-4-methyl-3-methoxycarbonyl-1-methyl-[1H]-pyrazole (Example H2) can also be converted into the corresponding cyano derivative in an analogous manner:

EXAMPLE H6 3-(4-chloro-2-fluoro-5-hydroxyphenyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole

3.04 g of lithium chloride.hydrate (LiCl.H₂O) are added at 22° C. to 2.8 g of 3-(4-chloro-2-fluoro-5-methoxyphenyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole (Example H5) in 90 ml of N,N-dimethylformamide. The reaction mixture is heated to reflux temperature and held for 4 days at this temperature, during which process some of the DMF (approx. 5 ml) is distilled off. The resulting reaction mixture is subsequently poured into dilute aqueous hydrochloric acid and extracted with dichloromethane. The organic phase which has been separated off is washed with water and saline, dried over anhydrous sodium sulfate and evaporated in vacuo. The residue obtained is purified over a silica gel column (eluent: ethyl acetate/hexane 1/1). This gives the desired product in a yield of 1.61 g (60.9% of theory).

1.92 g (68.3% of theory) of the desired 3-(2,4-dichloro-5-hydroxyphenyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole (Comp. No. I₃₆.103) are obtained in an analogous manner from 2.96 g of 3-(2,4-dichloro-5-methoxyphenyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole.

EXAMPLE H7 3-(4-chloro-2-fluoro-5-propargyloxyphenyl)-4-methyl-5-cyano-1-methyl-[1H]pyrazole

1.33 g of 3-(4-chloro-2-fluoro-5-hydroxyphenyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole (Example H6) are dissolved in 25 ml of acetone, and 1.38 g of potassium carbonate are added. The reaction mixture is stirred for 10 minutes at 22° C., and 0.89 g (0.56 ml) of propargyl bromide is then added dropwise with stirring, and stirring is continued for 5 hours at this temperature. The solvent is subsequently distilled off in vacuo and the residue is taken up in diethyl ether. After the etheric solution has been washed with water and saline and the solvent evaporated off, the desired product is obtained in a yield of 1.36 g (89.9% of theory).

1.38 g (86.4% of theory) of the desired 3-(2,4-dichloro-5-propargyloxyphenyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole (Comp. No. I₃.027) are obtained in a similar manner from 1.41 g of 3-(2,4-dichloro-5-hydroxyphenyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole.

EXAMPLE H8 3-(4-chloro-2-fluoro-5-iodophenyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole

5.86 g of isoamyl nitrite are added dropwise at a temperature of below 15° C. to a solution of 2.64 g of 3-(5-amino-4-chloro-2-fluoro-phenyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole in 54 g (16 ml) of diiodomethane. The reaction mixture is stirred for 14 hours at 22° C., and excess diiodomethane is evaporated in vacuo. All the diiodomethane is subsequently distilled off at 70-75° C./14 torr, and the crude product is purified over a silica gel column (eluent: ethyl acetate/hexane 1/5). The desired product is obtained in a yield of 1.88 g (50.2% of theory).

2.04 g (52.1% of theory) of the desired 3-(2,4-dichloro-5-iodophenyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole (Comp. No. I₃₆.111) are obtained in an analogous manner from 2.81 g of 3-(5-amino-2,4-dichlorophenyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole.

EXAMPLE H9 3-(4-chloro-2-fluoro-5-(2-chloro-2-carbethoxy)prop-1-yl-phenyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole

2.2 g of copper(II) chloride.hydrate, which had previously been dried in a microwave oven, is added to 50 ml of acetonitrile. To this stirred suspension there are first added 24.5 g (26.7 ml) of ethyl methacrylate. The mixture is then cooled to −5° C., 1.66 g of tert-butyl nitrite are added dropwise, and 2.84 g of 3-(5-amino-4-chloro-2-fluorophenyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole, dissolved in 70 ml of acetonitrile, are then added in the course of ½ to 1 hour at −5° C. to 0° C. This reaction mixture is stirred for 1 hour at 0° C. and subsequently for a further hour at 22° C., the solvent is evaporated, and the residue is dissolved in diethyl ether. This etheric solution is washed with water and then with saturated aqueous sodium bicarbonate solution and concentrated, and the residue is purified by silica gel chromatography (eluent: ethyl acetate/hexane 1/9). This gives 2.16 g (50.5% of theory) of the desired compound.

EXAMPLE H10 3-(4-chloro-2-fluoro-5-[(N,N-bisethanesulfonyl)amino]phenyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole

2.12 g of 3-(5-amino-4-chloro-2-fluorophenyl)-4-methyl-5-cyano-1-methyl-[1 H]-pyrazole are dissolved in 25 ml of dichloromethane, and 2.19 g (3.01 ml) of triethylamine are then added. This mixture is cooled to −15° C., and 2.37 g (1.74 ml) of ethanesulfonyl chloride are added dropwise. The mixture is subsequently slowly heated to 22° C., washed with dilute aqueous hydrochloric acid, dried over sodium sulfate and concentrated. The crude product obtained is purified by silica gel chromatography (eluent: ethyl acetate/hexane 1/2), yielding 3.05 g (85% of theory) of the desired product.

EXAMPLE H11 3-(4-chloro-2-fluoro-5-ethanesulfonamidophenyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole

6.5 ml of 2N sodium hydroxide solution are added dropwise to a solution of 2.93 g of 3-(4-chloro-2-fluoro-5-[(N,N-bisethanesulfonyl)amino]phenyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole (Example H10) in 15 ml of dioxane and the mixture is stirred for 1 hour at 22° C. The mixture is subsequently poured into ice/water mixture and extracted with ethyl acetate. The combined organic phases are washed with water and dried over sodium sulfate. After the mixture has been filtered and concentrated, 2.31 g (90.6% of theory) of the desired product are obtained.

EXAMPLE H12 3-(4-chloro-2-fluoro-5-[(N-allyl-N-ethanesulfonyl)amino]phenyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole

0.63 g of potassium carbonate is added to a solution of 1.08 g of 3-(4-chloro-2-fluoro-5-ethanesulfonamidophenyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole (Example H11) in 30 ml of tetrahydrofuran (THF). 0.55 g of allyl bromide is added dropwise to this suspension, with stirring, and the mixture is stirred first overnight at 22° C. and subsequently for another 8 hours at 40°-50° C. The solvent is evaporated and the resulting residue is purified over silica gel (eluent: ethyl acetate/hexane 1/2). This gives 1.19 g (99.5% of theory) of the desired product.

EXAMPLE H13 3-(4-chloro-2-fluoro-5-carbethoxyphenyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole

5.2 g of 3-(4-chloro-2-fluoro-5-iodophenyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole (Example H8), 60 ml of methanol, 2.8 g of triethylamine and 0.4 g of bis(triphenylphosphine)palladium(II) dichloride (PdCl₂(PPh₃)₂) are placed into a 100 ml pressurized container and stirred for 16 hours at a temperature of 100° C. and a carbon monoxide pressure of 10 megapascal (Mpa). The solvent is subsequently evaporated and the crude product which remains is purified over a silica gel column (eluent: ethyl acetate/hexane 1/5). This gives 3.1 g (69.3% of theory) of the desired product.

EXAMPLE H14 3-(4-chloro-2-fluoro-5-carboxyphenyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole

3.1 g of 3-(4-chloro-2-fluoro-5-carbethoxyphenyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole (Example H13) are dissolved in 22 ml of dioxane, and 10 ml of 2N aqueous sodium hydroxide solution are added dropwise at 22° C. The mixture is stirred until the reaction is complete, the solvent is evaporated, the resulting residue is dissolved in water and the solution is brought to pH 1using hydrochloric acid. The precipitate formed is filtered off and dried. This gives the desired product in a yield of 2.63 g (89.8% of theory).

EXAMPLE H15 3-(4-chloro-2-fluorophenyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole (isomer A) and 3-(4-chloro-2-fluorophenyl)-4-cyano-1,5-dimethyl-[1H]-pyrazole (isomer B)

16.3 g of 4-chloro-2-fluorophenylmethylhydrazonoyl bromide.hydrobromide are added to 275 ml of toluene and the mixture is stirred. 8.92 g of 2-bromo-2-butenonitrile are added to this stirred suspension, followed by the dropwise addition of 8.5 ml of triethylamine (exothermic). Stirring of the suspension is continued for 2 hours at 60° C. The mixture is cooled and then filtered, the solids are washed with toluene and the toluene phase is extracted with 1N aqueous hydrochloric acid, then washed with water and saline and dried over sodium sulfate. The solvent is evaporated and the resulting crude product is purified over a silica gel column (eluent: ethyl acetate/hexane 1/4). The products obtained are the desired isomer A in a yield of 7.68 g (65.4% of theory) and isomer B in a yield of 0.91 g (7.7% of theory).

EXAMPLE H16 3-(4-chloro-2-fluoro-5-(carboxylic acid-1-ethoxycarbonyl-1-methylethylester)phenyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole

2 drops of N,N-dimethylformamide (DMF) and then, dropwise, 1.01 g of oxalyl chloride are added to a stirred solution of 1.17 g of 3-(4-chloro-2-fluoro-5-carboxyphenyl)-4-methyl-5-cyano-1-methyl-[1H]-pyrazole (Example H14) in 30 ml of dry dichloromethane. This mixture is stirred for 1hour at 22° C. and subsequently refluxed for 10 minutes. The solvent and excess oxalyl chloride are evaporated and the resulting residue is dissolved in 30 ml of dry dichloromethane. A solution of 0.605 g of ethyl 2-hydroxyisobutyrate in 8 ml of pyridine is added dropwise to this solution, and this mixture is stirred overnight at 22° C. The solvent is subsequently evaporated, the resulting residue is dissolved in ethyl acetate, and this solution is washed first with water and then with saline and dried over sodium sulfate. The solvent is evaporated and the crude product is purified over a silica gel column (eluent: ethyl acetate/hexane 1/8). The desired product is obtained in a yield of 1.06 g (65.4% of theory).

The compounds listed in the tables which follow can also be prepared in an analogous manner.

In Tables 1to 6 and 8 to 10 which follow, certain structures I_(n), II₁, II₂, III₁, III₂, III_(n) or V_(n), for example I₁ to I₈ in Table 1 or I₃₃ to I₃₅ in Table 5, which have the same variations of substitutents, for example R₅ and R₆ in Table 1 or R₂, R₃, R₄, R₅ and R₇₂ in Table 5, are combined for the sake of simplicity.

Thus, in the abovementioned tables, all structures I_(n), or II₁, II₂, III₁, III₂, III_(n) or V_(n) which are mentioned in the captions of the tables where n=1 to 8 in the case of Table 1, are to be combined with the meanings mentioned in the tables. In Table 1, for example, I_(n).001 discloses each of the 8 specific compounds I₁.001, I₂.001, I₃.001, I₄.001, I₅.001, I₆.001, I₇.001 and I₈.001 in which R₅ and R₆ are in each case chlorine or hydrogen.

TABLE 1 Compounds of the formulae I₁ to I₈

Comp. No. I_(n) n = 1-8 R₅ R₆ 001 Cl H 002 Br H 003 CN H 004 I H 005 CH₃ H 006 Cl OCH₃ 007 Br OCH₃ 008 CN OCH₃ 009 I OCH₃ 010 CH₃ OCH₃ 011 Cl OCH₂CH₃ 012 Cl OCH₂CH₂CH₃ 013 Cl OCH(CH₃)₂ 014 Br OCH(CH₃)₂ 015 Cl OCH₂CHCH₂ 016 Br OCH₂CHCH₂ 017 CH₃ OCH₂CHCH₂ 018 CN OCH₂CHCH₂ 019 Cl OCH₂C(CH₃)CH₂ 020 Br OCH₂C(CH₃)CH₂ 021 CH₃ OCH₂C(CH₃)CH₂ 022 CN OCH₂C(CH₃)CH₂ 023 Cl OCH₂CClCH₂ 024 Br OCH₂CClCH₂ 025 Cl OCH(CH₃)CHCH₂ 026 CN OCH(CH₃)CHCH₂ 027 Cl OCH₂CCH 028 Br OCH₂CCH 029 CN OCH₂CCH 030 CH₃ OCH₂CCH 031 Cl OCH(CH₃)CCH 032 Br OCH(CH₃)CCH 033 Cl OCH₂C₆H₅ 034 Cl OCH₂CH₂OCH₂CH₃ 035 Br OCH₂CH₂OCH₂CH₃ 036 CN OCH₂CH₂OCH₂CH₃ 037 CH₃ OCH₂CH₂OCH₂CH₃ 038 Cl OCH₂CH₂OCH₂CH₂OCH₃ 039 Br OCH₂CH₂OCH₂CH₂OCH₃ 040 CN OCH₂CH₂OCH₂CH₂OCH₃ 041 CH₃ OCH₂CH₂OCH₂CH₂OCH₃ 042 Cl OCH(CH₃)CH₂OCH₃ 043 Cl OCH₂COOH 044 Cl OCH₂COOCH₂CH₃ 045 Cl OCH(CH₃)COOH 046 Br OCH(CH₃)COOH 047 Cl OCH(CH₃)COOCH₃ 048 Cl OCH(CH₃)COOCH₂CH₃ 049 Cl OCH(CH₃)COOCH₂C₆H₅ 050 Br OCH(CH₃)COOCH(CH₃)₂ 051 CN OCH(CH₃)COOCH₂CH₃ 052 Cl OCH(C₆H₅)COOH 053 Cl OCH(C₆H₅)COOCH₃ 054 Br OCH(C₆H₅)COOCH₂CH₃ 055 Cl OC(CH₃)₂COOH 056 Cl OC(CH₃)₂COOCH₂CH₃ 057 Br OCH₂CH₂COOH 058 Br OCH₂CH₂COOCH₃ 059 Cl SCH₃ 060 Cl SCH₂CHCH₂ 061 Cl SCH₂COOH 062 Cl SCH₂COOCH(CH₃)₂ 063 Cl SCH(CH₃)COOH₂CH₃ 064 Br SCH(C₆H₅)COOH 065 Cl NHSO₂CH₃ 066 Br NHSO₂CH₃ 067 CN NHSO₂CH₃ 068 Cl N(CH₃)SO₂CH₃ 069 Br N(CH₃)SO₂CH₃ 070 Cl N(CH₂CHCH₂)SO₂CH₃ 071 CN N(CH₂CHCH₂)SO₂CH₃ 072 Cl N(CH₂CCH)SO₂CH₃ 073 CN N(CH₂CCH)SO₂CH₃ 074 Cl N(CH₂C₆H₅)SO₂CH₃ 075 Cl NHSO₂CH₂CH₃ 076 CN NHSO₂CH₂CH₃ 077 Cl N(CH₂CHCH₂)SO₂CH₂CH₃ 078 Br N(CH₂CHCH₂)SO₂CH₂CH₃ 079 CN N(CH₂CHCH₂)SO₂CH₂CH₃ 080 Cl N(CH₂CCH)SO₂CH₂CH₃ 081 Cl NHSO₂CH(CH₃)₂ 082 CN NHSO₂CH(CH₃)₂ 083 Cl N(CH₂CCH)SO₂CH(CH₃)₂ 084 Br N(CH₂CHCH₂)SO₂CH(CH₃)₂ 085 Cl NHSO₂CF₃ 086 CN NHSO₂CF₃ 087 Cl N(CH₂CH₃)SO₂CF₃ 088 Cl N(CH₂CHCH₂)SO₂CF₃ 089 Br N(CH₂CHCH₂)SO₂CF₃ 090 Cl N(CH₂CCH)SO₂CF₃ 091 Br N(CH₂CCH)SO₂CF₃ 092 CN N(CH₂CCH)SO₂CF₃ 093 CH₃ N(CH₂CCH)SO₂CF₃ 094 Cl CH₂CHClCOOH 095 Br CH₂CHClCOOH 096 CN CH₂CHClCOOH 097 CH₃ CH₂CHClCOOH 098 Cl CH₂CHClCOOCH₃ 099 Br CH₂CHClCOOCH₃ 100 Cl CH₂CHClCOOCH₂CH₃ 101 Br CH₂CHClCOOCH₂CH₃ 102 CN CH₂CHClCOOCH₂CH₃ 103 CH₃ CH₂CHClCOOCH₂CH₃ 104 Cl CH₂CHClCOOCH₂C₆H₅ 105 Cl CHClCHClCOOCH₂CH₃ 106 Cl CH₂CHBrCOOH 107 Cl CH₂CHBrCOOCH₃ 108 Cl CH₂CHClCOOCH₂CH₃ 109 Cl CH₂CH(CH₃)COOCH₃ 110 Cl CH₂CH(CH₃)COOH 111 Cl CH(CH₃)CH₂COOCH₂CH₃ 112 Br CH(CH₃)CH₂COOCH₂CH₃ 113 Cl CH₂CH₂COOH 114 Cl CH₂CH₂COOCH₃ 115 Br CH₂CH₂COOCH₃ 116 CH₃ CH₂CH₂COOCH₃ 117 Cl CH₂C(CH₃)ClCOOH 118 Cl CH₂C(CH₃)ClCOOCH₂CH₃ 119 Cl CH₂CH(N₃)COOCH₃ 120 Br CH₂CH(N₃)COOCH₂CH₃ 121 Cl CH₂CHClCOOCH₂CHCH₂ 122 Cl CH₂CHClCOOCH₂C₆H₅ 123 Cl CH₂CHCH₂ 124 Br CH₂CHCH₂ 125 CN CH₂CHCH₂ 126 CH₃ CH₂CHCH₂ 127 Cl CHCH₂ 128 Br CHCH₂ 129 CH₃ CHCH₂ 130 Cl COOH 131 Br COOH 132 CN COOH 133 CH₃ COOH 134 Cl COOCH₃ 135 Br COOCH₃ 136 Cl COOCH₂CH₃ 137 Br COOCH₂CH₃ 138 CN COOCH₂CH₃ 139 CH₃ COOCH₂CH₃ 140 Cl COOCH(CH₃)₂ 141 Br COOCH(CH₃)₂ 142 CN COOCH(CH₃)₂ 143 CH₃ COOCH(CH₃)₂ 144 Cl COOCH₂CHCH₂ 145 Cl CONHCH₂CHCH₂ 146 Cl CONHCH₂CCH 147 Cl CON(CH₂CH₃)₂ 148 Br CONHCH₂C₆H₅ 149 Br CON(CH₂C₆H₅)2 150 Cl COOCH₂C₆H₅ 151 Cl COOC(CH₃)₂COOH 152 Br COOC(CH₃)₂COOH 153 CN COOC(CH₃)₂COOH 154 CH₃ COOC(CH₃)₂COOH 155 Cl COOC(CH₃)₂COOCH₃ 156 Br COOC(CH₃)₂COOCH₃ 157 CN COOC(CH₃)₂COOCH₃ 158 CH₃ COOC(CH₃)₂COOCH₃ 159 Cl COOC(CH₃)₂COOCH₂CH₃ 160 Br COOC(CH₃)₂COOCH₂CH₃ 161 Cl COOC(CH₃)₂COOCH₂CHCH₂ 162 Br COOC(CH₃)₂COOCH₂CHCH₂ 163 CN COOC(CH₃)₂COOCH₂CHCH₂ 164 CH₃ COOC(CH₃)₂COOCH₂CHCH₂ 165 Cl COOC(CH₃)₂COOCH₂C₆H₅ 166 Br COOC(CH₃)₂COOCH₂C₆H₅ 167 Cl COOC(CH₃)₂COOCH₂CH₂OCH₂CH₃ 168 Br COOC(CH₃)₂COOCH₂CH₂OCH₂CH₃ 169 CN COOC(CH₃)₂COOCH₂CH₂OCH₂CH₃ 170 CH₃ COOC(CH₃)₂COOCH₂CH₂OCH₂CH₃ 171 Cl COOCH(C₆H₅)COOH 172 Br COOCH(C₆H₅)COOH 173 CH₃ COOCH(C₆H₅)COOH 174 Cl COOCH(C₆H₅)COOCH₃ 175 Br COOCH(C₆H₅)COOCH₃ 176 Cl COOCH(C₆H₅)COOCH₂CH₃ 177 Br COOCH(C₆H₅)COOCH₂CH₃ 178 CN COOCH(C₆H₅)COOCH₂CH₃ 179 Cl COOCH(C₆H₅)COOCH₂CHCH₂ 180 Cl COOCH(C₆H₅)COOCH₂C₆H₅ 181 Cl COOCH₂CH(CH₃)COOH 182 Br COOCH₂CH(CH₃)COOH 183 CH₃ COOCH₂CH(CH₃)COOH 184 CN COOCH₂CH(CH₃)COOH 185 Cl COOCH₂CH(CH₃)COOCH₂CH₃ 186 Br COOCH₂CH(CH₃)COOCH₂CH₃ 187 CN COOCH₂CH(CH₃)COOCH₂CH₃ 188 CH₃ COOCH₂CH(CH₃)COOCH₂CH₃ 189 Cl (S)—COOCH(CH₃)CH₂COOCH₂CH₃ 190 Br (S)—COOCH(CH₃)CH₂COOCH₂CH₃ 191 Cl COOC(CH₃)₂COCH₃ 192 Br COOC(CH₃)₂COCH₃ 193 CN COOC(CH₃)₂COCH₃ 194 Cl COOC(CH₃)₂CONHCH₂CCH 195 Br COOC(CH₃)₂CONHCH₂CCH 196 Cl COOC(CH₃)₂CON(CH₂CH₃)₂ 197 CH₃ COOC(CH₃)₂CON(CH₂CH₃)₂ 198 Cl COOC(CH₃)₂CON(CH₂C₆H₅)2 199 Cl COOCH(CH₃)CONHCH₂CHCH₂ 200 Br COOCH(CH₃)CONHCH₂CHCH₂ 201 Cl COOCH(CH₃)CONHCH₂CCH 202 Br COOCH(CH₃)CONHCH₂CCH 203 CN COOCH(CH₃)CONHCH₂CCH 204 CH₃ COOCH(CH₃)CONHCH₂CCH 205 Cl COOCH(CH₃)CON(CH₃)₂ 206 Cl COOCH(C₆H₅)CONHCH₂CCH 207 Cl COOCH(C₆H₅)CON(CH₂CH₃)₂ 208 Br COOCH(C₆H₅)CON(CH₂CH₃)₂ 209 Cl COSCH(CH₃)COOH 210 Br COSCH(CH₃)COOH 211 Cl COSCH(CH₃)COOCH₃ 212 Cl COSCH(CH₃)COOCH₂CHCH₂ 213 Br COSCH(CH₃)COOCH₂CHCH₂ 214 Cl COSCH(CH₃)CONHCH₂CCH 215 Cl CONHC(CH₃)₂COOH 216 Cl CON(CH₃)C(CH₃)₂COOCH₂CH₃ 217 Cl CON(SO₂CH₃)CH(CH₃)COOH 218 Cl CON(SO₂CH₃)CH(CH₃)COOCH₂CH₃ 219 Cl COOC(CH₃)₂COOC₂H₅ 220 Cl NHSO₂C₂H₅ 221 Cl N(CH₂CCH)SO₂C₂H₅ 222 Cl N(SO₂CH₃)₂ 223 Cl N(SO₂C₂H₅)2 224 Br N(SO₂CH₃)₂

TABLE 2 Compounds of the formulae I₉ to I₂₁ (I₉)

(I₁₀)

(I₁₁)

(I₁₂)

(I₁₃)

(I₁₄)

(I₁₅)

(I₁₆)

(I₁₇)

(I₁₈)

(I₁₉)

(I₂₀)

(I₂₁)

Comp. No. I_(n) n = 9-21 R₅ R₆ 001 Cl H 002 Br H 003 CN H 004 CH₃ H 005 Cl OCH₃ 006 Br OCH₃ 007 CN OCH₃ 008 CH₃ OCH₃ 009 Cl OCH₂CCH 010 Br OCH₂CCH 011 CN OCH₂CCH 012 CH₃ OCH₂CCH 013 Cl OCH(CH₃)₂ 014 Cl OCH(CH₃)CCH 015 Cl OCH₂CHCH₂ 016 Br OCH₂CHCH₂ 017 Cl OCH₂C(CH₃)CH₂ 018 Cl OCH₂CClCH₂ 019 Cl OCH(CH₃)CHCH₂ 020 Cl OCH(CH₃)COOH 021 Br OCH(CH₃)COOH 022 Cl OCH(CH₃)COOCH₃ 023 Br OCH(CH₃)COOCH₂CH₃ 024 CH₃ OCH(CH₃)COOCH₂CHCH₂ 025 CN OCH(CH₃)COOCH₂C₆H₅ 026 Cl OCH(C₆H₅)COOH 027 Br OCH(C₆H₅)COOH 028 Cl OCH(C₆H₅)COOCH₃ 029 Br OCH(C₆H₅)COOCH(CH₃)₂ 030 CH₃ OCH(C₆H₅)COOCH₂C₆H₅ 031 CN OCH(C₆H₅)COOCH₂CHCH₂ 032 Cl SCH₃ 033 Cl SCH(CH₃)₂ 034 CH₃ SCH(CH₃)₂ 035 Br NH(CH₂CHCH₂) 036 CH₃ N(CH₂CH₃)₂ 037 Cl N(SO₂CH₃)CH₃ 038 Cl N(SO₂CH₃)CH₂CHCH₂ 039 Br N(SO₂CH₂CH₃)CH₂CCH 040 CH₃ N(SO₂CF₃)CH₂CH₃ 041 Cl N(SO₂CF₃)CH(CH₃)CHCH₂ 042 Cl CHCH₂ 043 Cl CH₂CHCH₂ 044 Br CH₂CHCH₂ 045 Cl CH₂CHClCOOH 046 Br CH₂CHClCOOH 047 Cl CH₂CHClCOOCH₃ 048 Cl CH₂CHClCOCH₂CH₃ 049 Br CH₂CHClCOCH₂CH₃ 050 CN CH₂CHClCOCH₂CH₃ 051 CH₃ CH₂CHClCOCH₂CH₃ 052 Cl CH₂CHClCOOCH₂CHCH₂ 053 Br CH₂CHClCOOCH₂C₆H₅ 054 Cl CH₂CH(CH₃)COOH 055 Br CH₂CH(CH₃)COOCH₃ 056 Cl CH₂CH₂COOCH₃ 057 Cl COOH 058 Br COOH 059 CH₃ COOCH₃ 060 Cl COOCH₂CH₃ 061 Br COOCH₂CH₃ 062 CH₃ COOCH₂CHCH₂ 063 Cl COOCH(CH₃)₂ 064 CN COOCH₂C₆H₅ 065 Cl COOCH(CH₃)COOH 066 Br COOCH(CH₃)COOCH₃ 067 Cl COOCH(CH₃)COOCH₂CHCH₂ 068 Cl COOCH(C₆H₅)COOH 069 Br COOCH(C₆H₅)COOCH₃ 070 CH₃ COOCH(C₆H₅)COOCH(CH₃)₂ 071 Cl COOC(CH₃)₂COOH 072 CH₃ COOC(CH₃)₂COOH 073 Br COOC(CH₃)₂COOCH₃ 074 Cl COOC(CH₃)₂COOCH₂CH₃ 075 Br COOC(CH₃)₂COOCH₂CH₃ 076 CH₃ COOC(CH₃)₂COOCH₂CH₃ 077 CN COOC(CH₃)₂COOCH₂CCH 078 Cl COOC(CH₃)₂CONH(CH₂CCH) 079 Br COOC(CH₃)₂CON(CH₂CHCH₂)₂ 080 Cl COOC(CH₃)₂CONH₂ 081 Cl COOCH(CH₃)CH₂COOCH₃ 082 Cl COSCH(CH₃)COOH 083 Cl COSCH(CH₃)COOCH₂CH₃

TABLE 3 Compounds of the formulae I₂₂ to I₂₈ (I₂₂)

(I₂₃)

(I₂₄)

(I₂₅)

(I₂₆)

(I₂₇)

(I₂₈)

Comp No. I_(n) n = 22-28 X₂ R₆₁ 001 O H 002 S H 003 O CH₃ 004 O CH₂CHCH₂ 005 S CH₂CHCH₂ 006 O CH(CH₃)CHCH₂ 007 S CH(CH₃)CHCH₂ 008 O CH(CH₃)₂ 009 O CH₂CCH 010 O CH(CH₃)CCH 011 S CH₂CCH 012 O CH₂C₆H₅ 013 O CH₂COOH 014 S CH₂COOH 015 O CH₂COOCH₃ 016 O CH₂COOCH₂CH₃ 017 S CH₂COOCH₂CH₃ 018 O CH(CH₃)COOH 019 O CH(CH₃)COOCH₃ 020 O CH(CH₃)COOCH₂CH₃ 021 O CH(CH₃)COOCH₂CHCH₂ 022 O CH(CH₃)COOCH₂C₆H₅ 023 O CH(C₆H₅)COOH 024 O CH(C₆H₅)COOCH₂CH₃ 025 O CH₂CH₂OCH₂CH₃ 026 S CH₂CH₂OCH₂CH₃ 027 O CH₂OCH₃

TABLE 4 Compounds of the formulae I₂₉ to I₃₂ (I₂₉)

(I₃₀)

(I₃₁)

(I₃₂)

Comp. No. I_(n) n = 29-32 R₄ R₆₁ 001 F H 002 F CH₃ 003 F CH₂CH₃ 004 F CH(CH₃)₂ 005 F CH₂CHCH₂ 006 F CH(CH₃)CHCH₂ 007 F CH₂CCH 008 F CH(CH₃)CCH 009 F CH₂C₆H₅ 010 F CH₂COOH 011 F CH₂COOCH₃ 012 F CH₂CH(CH₃)₂ 013 F CH(CH₃)COOH 014 F CH(CH₃)COOCH₃ 015 F CH(CH₃)COOCH₂CH₃ 016 F CH(CH₃)COOCH₂C₆H₅ 017 F CH(C₆H₅)COOH 018 F CH(C₆H₅)COOCH₂CHCH₂ 019 Cl H 020 Cl CH₂CH₃ 021 Cl CH(CH₃)₂ 022 Cl CH₂CHCH₂ 023 Cl CH₂CCH 024 Cl CH₂COOH 025 Cl CH₂COOCH₃ 026 Cl CH₂COOCH₂CHCH₂ 027 Cl CH(CH₃)COOH 028 Cl CH(CH₃)COOCH₂CH₃ 029 CH₃ H 030 CH₃ CH₂CCH 031 CH₃ CH₂COOH 032 CH₃ CH₂COOCH₂CH₃ 033 CH₃ CH(CH₃)COOH 034 H H 035 H CH(CH₃)₂ 036 H CH₂CCH 037 H CH₂COOH

TABLE 5 Compounds of the formulae I₃₃ to I₃₅ (I₃₃)

(I₃₄)

(I₃₅)

Comp. No. I_(n) n = 33-35 R₃ R₂ R₄ R₅ R₇₂ 001 CH₃ CN F Cl H 002 CH₃ CN F Cl CH₃ 003 CH₃ CN F Cl CH₂CH₃ 004 CH₃ CN F Cl CH₂Cl 005 CH₃ CN F Cl CH₂OH 006 CH₃ CN F Cl CH₂OCH₃ 007 CH₃ CN F Cl CH₂O(O)CCH₃ 008 CH₃ CN F Cl CH₂O(O)CCH₂Cl 009 CH₃ CN F Cl COOH 010 CH₃ CN F Cl COOCH₃ 011 CH₃ CN F Cl COOCH₂CH₃ 012 CH₃ CN F Cl COOCH₂CHCH₂ 013 CH₃ CN F Cl COOCH₂C₆H₅ 014 CH₃ CN F Cl COOCH₂CCH 015 CH₃ CN F Cl CONH₂ 016 CH₃ CN F Cl CON(CH₂CH₃)₂ 017 CH₃ CN F Cl CONHCH₂CCH 018 CH₃ CN F Br CH₃ 019 CH₃ CN F Br CH₂OH 020 CH₃ CN F Br CH₂Br 021 CH₃ CN F Br COOH 022 CH₃ CN F Br COOCH₃ 023 CH₃ CN F Br COOCH(CH₃)₂ 024 CH₃ CN F Br COOCH₂CHCH₂ 025 CH₃ CN F Br CONHCH₂CHCH₂ 026 CH₃ CN Cl Cl CH₃ 027 CH₃ CN Cl Cl CH₂OH 028 CH₃ CN Cl Cl CH₂O(O)CCH₃ 029 CH₃ CN Cl Cl COOH 030 CH₃ CN Cl Cl COOCH₂CH₃ 031 CH₃ CN Cl Cl COOCH₂C₆H₅ 032 CH₃ CN Cl Cl CON(CH₂CHCH₂)₂ 033 CH₃ CN F CH₃ CH₂OH 034 CH₃ CN F CH₃ CH₂Cl 035 CH₃ CN F CH₃ COOH 036 CH₃ CN F CH₃ COOCH₂CCH 037 CH₃ CN F CN CH₃ 038 CH₃ CN F CN CH₂O(O)CCH₃ 039 CH₃ CN F CN COOH 040 CH₃ CN F CN COOCH₃ 041 CH₃ CN F CN CONHCH₃ 042 CH₃ CN Cl CH₃ CH₂OH 043 CH₃ CN Cl CH₃ COOH 044 CH₃ CN Cl CN CH₂OH 045 CH₃ CN Cl CN COOH 046 CH₃ CN Cl Br CH₂OH 047 CH₃ CN Cl Br COOCH₂CH₃ 048 CH₂CH₃ CN F Cl CH₃ 049 CH₂CH₃ CN F Cl CH₂OH 050 CH₂CH₃ CN F Cl CH₂Cl 051 CH₂CH₃ CN F Cl CH₂OCH₃ 052 CH₂CH₃ CN F Cl COOCH(CH₃)₂ 053 CH₂CH₃ CN F Cl COOH 054 CH₂CH₃ CN F Cl CH₂CH₃ 055 CH₃ CSNH₂ F Cl CH₃ 056 CH₃ CSNH₂ F Cl CH₂OH 057 CH₃ CSNH₂ F Cl CH₂O(O)CCH₃ 058 CH₃ CSNH₂ F Cl COOH 059 CH₃ CSNH₂ F Cl COOCH₃ 060 CH₃ CSNH₂ F Cl CONHCH₃ 061 CH₃ CSNH₂ F Cl CON(CH₂CH₃)₂ 062 CH₃ CSNH₂ F Cl CONH₂ 063 CH₃ CSNH₂ Cl Cl CH₂OH 064 CH₃ CSNH₂ Cl Cl CH₃ 065 CH₃ CSNH₂ Cl Cl COOH 066 CH₃ CSNH₂ Cl Cl COOCH₂CH₃ 067 CH₃ CSNH₂ F CN CH₃ 068 CH₃ CSNH₂ F CN COOCH₂CHCH₂ 069 CH₃ CSNH₂ F Br CH₃ 070 CH₃ CSNH₂ F Br CH₂OH 071 CH₃ CSNH₂ F Br COOCH₃ 072 CH₃ CSNH₂ F CH₃ CH₂OH 073 CH₃ CSNH₂ F CH₃ COOCH₂CCH 074 CH₃ CSNH₂ Cl Cl CH₂OH 075 CH₃ CSNH₂ Cl Cl COOCH₃ 076 CH₂CH₃ CSNH₂ F Cl CH₃ 077 CH₂CH₃ CSNH₂ F Cl CH₂OH 078 CH₂CH₃ CSNH₂ F Cl CH₂Cl 079 CH₂CH₃ CSNH₂ F Cl COOH 080 CH₂CH₃ CSNH₂ Cl Cl CH₂O(O)CCH₃ 081 CH(CH₃)₂ CN F Cl CH₃ 082 CH(CH₃)₂ CN F Cl CH₂Cl 083 CH(CH₃)₂ CN F Cl COOH 084 CH(CH₃)₂ CN F Cl COOCH₂CHCH₂ 085 CH(CH₃)₂ CN F Br CH₂OH 086 CH(CH₃)₂ CN F Br COOH 087 CH₃ CN H Cl CH₂OH 088 CH₃ CN H Cl COOH 089 CH₃ CN H Cl COOCH₃ 090 CH₃ CN H Cl Cl 091 CH₂CH₃ CN H Cl CH₂OH 092 CH₃ CN H Br CH₂OH 093 CH₂CH₃ CN H Br COOCH₃

TABLE 6 Compounds of the formulae V₁, V₂, II₁ and III₁

Comp. No. V_(n) or II₁ and III₁ n = 1 or 2 R₃ R₄ R₅ R₆ 001 CH₃ F Cl H 002 CH₃ F Br H 003 CH₃ F CN H 004 CH₃ F CH₃ H 005 CH₃ Cl Cl H 006 CH₃ Cl Br H 007 CH₃ Cl CN H 008 CH₃ Cl CH₃ H 009 CH₃ F F H 010 CH₂CH₃ F Cl H 011 CH₂CH₃ F Br H 012 CH₂CH₃ F CN H 013 CH₂CH₃ F CH₃ H 014 CH₂CH₃ Cl Cl H 015 CH₂CH₃ Cl Br H 016 CH₂CH₃ Cl CN H 017 CH₂CH₃ Cl CH₃ H 018 CH₂CH₃ F F H 019 CH(CH₃)₂ F Cl H 020 CH(CH₃)₂ F Br H 021 CH(CH₃)₂ F CN H 022 CH(CH₃)₂ F CH₃ H 023 CH(CH₃)₂ Cl Cl H 024 CH(CH₃)₂ Cl Br H 025 CH(CH₃)₂ Cl CN H 026 CH(CH₃)₂ Cl CH₃ H 027 CH(CH₃)₂ F F H 028 CH₃ F NO₂ H 029 CH₃ Cl NO₂ H 030 CH₂CH₃ F NO₂ H 031 CH₂CH₃ Cl NO₂ H 032 CH(CH₃)₂ F NO₂ H 033 CH(CH₃)₂ Cl NO₂ H 034 CH₃ F NH₂ H 035 CH₃ Cl NH₂ H 036 CH₂CH₃ F NH₂ H 037 CH₂CH₃ Cl NH₂ H 038 CH(CH₃)₂ F NH₂ H 039 CH(CH₃)₂ Cl NH₂ H 040 CH₃ F H F 041 CH₂CH₃ F H F 042 CH(CH₃)₂ F H F 043 CH₃ F OH H 044 CH₂CH₃ F OH H 045 CH(CH₃)₂ F OH H 046 CH₃ F OCH₃ H 047 CH₂CH₃ F OCH₃ H 048 CH(CH₃)₂ F OCH₃ H 049 CH₃ Cl OH H 050 CH₂CH₃ Cl OH H 051 CH(CH₃)₂ Cl OH H 052 CH₃ Cl OCH₃ H 053 CH₂CH₃ Cl OCH₃ H 054 CH(CH₃)₂ Cl OCH₃ H 055 CH₃ F OCH₂COOCH₃ NO₂ 056 CH₂CH₃ F OCH₂COOCH₃ NO₂ 057 CH₃ Cl OCH₂COOCH₃ NO₂ 058 CH₂CH₃ Cl OCH₂COOCH₃ NO₂ 059 CH₃ F Cl OH 060 CH₂CH₃ F Cl OH 061 CH(CH₃)₂ F Cl OH 062 CH₃ Cl Cl OH 063 CH₂CH₃ Cl Cl OH 064 CH₃ F Br OH 065 CH₃ F CH₃ OH 066 CH₃ F CN OH 067 CH₂CH₃ F Br OH 068 CH₂CH₃ F CH₃ OH 069 CH₂CH₃ F CN OH 070 CH₃ Cl CN OH 071 CH₃ F Cl OCH₃ 072 CH₂CH₃ F Cl OCH₃ 073 CH(CH₃)₂ F Cl OCH₃ 074 CH₃ Cl Cl OCH₃ 075 CH₂CH₃ Cl Cl OCH₃ 076 CH₃ F Br OCH₃ 077 CH₃ F CH₃ OCH₃ 078 CH₃ F CN OCH₃ 079 CH₂CH₃ F Br OCH₃ 080 CH₂CH₃ F CH₃ OCH₃ 081 CH₂CH₃ F CN OCH₃ 082 CH₃ Cl CN OCH₃ 083 CH₃ F Cl OCH₂CHCH₂ 084 CH₂CH₃ F Cl OCH₂CHCH₂ 085 CH(CH₃)₂ F Cl OCH₂CHCH₂ 086 CH₃ Cl Cl OCH₂CHCH₂ 087 CH₂CH₃ Cl Cl OCH₂CHCH₂ 088 CH₃ F Br OCH₂CHCH₂ 089 CH₃ F CH₃ OCH₂CHCH₂ 090 CH₃ F CN OCH₂CHCH₂ 091 CH₂CH₃ F Br OCH₂CHCH₂ 092 CH₂CH₃ F CH₃ OCH₂CHCH₂ 093 CH₂CH₃ F CN OCH₂CHCH₂ 094 CH₃ Cl CN OCH₂CHCH₂ 095 CH₃ F Cl OCH₂C(CH₃)CH₂ 096 CH₂CH₃ F Cl OCH₂C(CH₃)CH₂ 097 CH(CH₃)₂ F Cl OCH₂C(CH₃)CH₂ 098 CH₃ Cl Cl OCH₂C(CH₃)CH₂ 099 CH₂CH₃ Cl Cl OCH₂C(CH₃)CH₂ 100 CH₃ F Br OCH₂C(CH₃)CH₂ 101 CH₃ F CH₃ OCH₂C(CH₃)CH₂ 102 CH₃ F CN OCH₂C(CH₃)CH₂ 103 CH₂CH₃ F Br OCH₂C(CH₃)CH₂ 104 CH₂CH₃ F CH₃ OCH₂C(CH₃)CH₂ 105 CH₂CH₃ F CN OCH₂C(CH₃)CH₂ 106 CH₃ Cl CN OCH₂C(CH₃)CH₂ 107 CH₃ F Cl OCH₂CClCH₂ 108 CH₂CH₃ F Cl OCH₂CClCH₂ 109 CH₃ F F NO₂ 110 CH₂CH₃ F F NO₂ 111 CH(CH₃)₂ F F NO₂ 112 CH₃ F Cl NO₂ 113 CH₂CH₃ F Cl NO₂ 114 CH(CH₃)₂ F Cl NO₂ 115 CH₃ Cl Cl NO₂ 116 CH₂CH₃ Cl Cl NO₂ 117 CH₃ F Br NO₂ 118 CH₃ F CH₃ NO₂ 119 CH₃ F CN NO₂ 120 CH₂CH₃ F Br NO₂ 121 CH₂CH₃ F CH₃ NO₂ 122 CH₂CH₃ F CN NO₂ 123 CH₃ Cl CN NO₂ 124 CH₃ F OH NO₂ 125 CH₂CH₃ F OH NO₂ 126 CH₃ Cl OH NO₂ 127 CH₃ F Cl NH₂ 128 CH₂CH₃ F Cl NH₂ 129 CH(CH₃)₂ F Cl NH₂ 130 CH₃ Cl Cl NH₂ 131 CH₂CH₃ Cl Cl NH₂ 132 CH₃ F Br NH₂ 133 CH₃ F CH₃ NH₂ 134 CH₃ F CN NH₂ 135 CH₂CH₃ F Br NH₂ 136 CH₂CH₃ F CH₃ NH₂ 137 CH₂CH₃ F CN NH₂ 138 CH₃ Cl CN NH₂ 139 CH₃ F Cl Br 140 CH₂CH₃ F Cl Br 141 CH(CH₃)₂ F Cl Br 142 CH₃ Cl Cl Br 143 CH₂CH₃ Cl Cl Br 144 CH₃ F Br Br 145 CH₃ F CH₃ Br 146 CH₃ F CN Br 147 CH₂CH₃ F Br Br 148 CH₂CH₃ F CH₃ Br 149 CH₂CH₃ F CN Br 150 CH₃ Cl CN Br 151 CH₃ F Cl I 152 CH₂CH₃ F Cl I 153 CH(CH₃)₂ F Cl I 154 CH₃ Cl Cl I 155 CH₂CH₃ Cl Cl I 156 CH₃ F Br I 157 CH₃ F CH₃ I 158 CH₃ F CN I 159 CH₂CH₃ F Br I 160 CH₂CH₃ F CH₃ I 161 CH₂CH₃ F CN I 162 CH₃ Cl CN I 163 CH₃ F Cl OSO₂CF₃ 164 CH₂CH₃ F Cl OSO₂CF₃ 165 CH(CH₃)₂ F Cl OSO₂CF₃ 166 CH₃ Cl Cl OSO₂CF₃ 167 CH₂CH₃ Cl Cl OSO₂CF₃ 168 CH₃ F Br OSO₂CF₃ 169 CH₃ F CH₃ OSO₂CF₃ 170 CH₃ F CN OSO₂CF₃ 171 CH₂CH₃ F Br OSO₂CF₃ 172 CH₂CH₃ F CH₃ OSO₂CF₃ 173 CH₂CH₃ F CN OSO₂CF₃ 174 CH₃ Cl CN OSO₂CF₃ 175 CH₃ F Cl COOH 176 CH₂CH₃ F Cl COOH 177 CH(CH₃)₂ F Cl COOH 178 CH₃ Cl Cl COOH 179 CH₂CH₃ Cl Cl COOH 180 CH₃ F Br COOH 181 CH₃ F CH₃ COOH 182 CH₃ F CN COOH 183 CH₂CH₃ F Br COOH 184 CH₂CH₃ F CH₃ COOH 185 CH₂CH₃ F CN COOH 186 CH₃ Cl CN COOH 187 CH₃ F Cl COOCH₂CH₃ 188 CH₂CH₃ F Cl COOCH₂CH₃ 189 CH(CH₃)₂ F Cl COOCH₂CH₃ 190 CH₃ Cl Cl COOCH₂CH₃ 191 CH₂CH₃ Cl Cl COOCH₂CH₃ 192 CH₃ F Br COOCH₂CH₃ 193 CH₃ F CH₃ COOCH₂CH₃ 194 CH₃ F CN COOCH₂CH₃ 195 CH₂CH₃ F Br COOCH₂CH₃ 196 CH₂CH₃ F CH₃ COOCH₂CH₃ 197 CH₂CH₃ F CN COOCH₂CH₃ 198 CH₃ Cl CN COOCH₂CH₃ 199 CH₃ F Cl COOCH₂C₆H₅ 200 CH₂CH₃ F Cl COOCH₂C₆H₅ 201 CH(CH₃)₂ F Cl COOCH₂C₆H₅ 202 CH₃ Cl Cl COOCH₂C₆H₅ 203 CH₂CH₃ Cl Cl COOCH₂C₆H₅ 204 CH₃ F Br COOCH₂C₆H₅ 205 CH₃ F CH₃ COOCH₂C₆H₅ 206 CH₃ F CN COOCH₂C₆H₅ 207 CH₂CH₃ F Br COOCH₂C₆H₅ 208 CH₂CH₃ F CH₃ COOCH₂C₆H₅ 209 CH₂CH₃ F CN COOCH₂C₆H₅ 210 CH₃ Cl CN COOCH₂C₆H₅ 211 CH₃ F Cl CH₃ 212 CH₂CH₃ F Cl CH₃ 213 CH(CH₃)₂ F Cl CH₃ 214 CH₃ Cl Cl CH₃ 215 CH₂CH₃ Cl Cl CH₃ 216 CH₃ F Br CH₃ 217 CH₃ F CH₃ CH₃ 218 CH₃ F CN CH₃ 219 CH₂CH₃ F Br CH₃ 220 CH₂CH₃ F CH₃ CH₃ 221 CH₂CH₃ F CN CH₃ 222 CH₃ Cl CN CH₃ 223 CH₃ F Cl CHO 224 CH₂CH₃ F Cl CHO 225 CH(CH₃)₂ F Cl CHO 226 CH₃ Cl Cl CHO 227 CH₂CH₃ Cl Cl CHO 228 CH₃ F Br CHO 229 CH₃ F CH₃ CHO 230 CH₃ F CN CHO 231 CH₂CH₃ F Br CHO 232 CH₂CH₃ F CH₃ CHO 233 CH₂CH₃ F CN CHO 234 CH₃ Cl CN CHO 235 CH₃ F Cl NH₂ 236 CH₂CH₃ F Cl NH₂ 237 CH(CH₃)₂ F Cl NH₂ 238 CH₃ Cl Cl NH₂ 239 CH₂CH₃ Cl Cl NH₂ 240 CH₃ F Br NH₂ 241 CH₃ F CH₃ NH₂ 242 CH₃ F CN NH₂ 243 CH₂CH₃ F Br NH₂ 244 CH₂CH₃ F CH₃ NH₂ 245 CH₂CH₃ F CN NH₂ 246 CH₃ Cl CN NH₂ 247 CH₃ F Cl CH₃ 248 CH₂CH₃ F Cl CH₃ 249 CH(CH₃)₂ F Cl CH₃ 250 CH₃ Cl Cl CH₃ 251 CH₂CH₃ Cl Cl CH₃ 252 CH₃ F Br CH₃ 253 CH₃ F CH₃ CH₃ 254 CH₃ F CN CH₃ 255 CH₂CH₃ F Br CH₃ 256 CH₂CH₃ F CH₃ CH₃ 257 CH₂CH₃ F CN CH₃ 258 CH₃ Cl CN CH₃ 259 CH₃ F NO₂ OH 260 CH₂CH₃ F NO₂ OH 261 CH(CH₃)₂ F NO₂ OH 262 CH₃ Cl NO₂ OH 263 CH₂CH₃ Cl NO₂ OH 264 CH₃ F NO₂ OCH₃ 265 CH₂CH₃ F NO₂ OCH₃ 266 CH(CH₃)₂ F NO₂ OCH₃ 267 CH₃ Cl NO₂ OCH₃ 268 CH₂CH₃ Cl NO₂ OCH₃ 269 CH₃ F NO₂ Br 270 CH₂CH₃ F NO₂ Br 271 CH(CH₃)₂ F NO₂ Br 272 CH₃ Cl NO₂ Br 273 CH₂CH₃ Cl NO₂ Br 274 CH₃ F NO₂ COOH 275 CH₂CH₃ F NO₂ COOH 276 CH(CH₃)₂ F NO₂ COOH 277 CH₃ Cl NO₂ COOH 278 CH₂CH₃ Cl NO₂ COOH 279 CH₃ F NO₂ CH₃ 280 CH₂CH₃ F NO₂ CH₃ 281 CH(CH₃)₂ F NO₂ CH₃ 282 CH₃ Cl NO₂ CH₃ 283 CH₂CH₃ Cl NO₂ CH₃ 284 CH₃ F NO₂ Cl 285 CH₂CH₃ F NO₂ Cl 286 CH(CH₃)₂ F NO₂ Cl 287 CH₃ Cl NO₂ Cl 288 CH₂CH₃ Cl NO₂ Cl 289 CH₃ F NO₂ NH₂ 290 CH₂CH₃ F NO₂ NH₂ 291 CH(CH₃)₂ F NO₂ NH₂ 292 CH₃ Cl NO₂ NH₂ 293 CH₂CH₃ Cl NO₂ NH₂ 294 CH₂CH₃ F NH₂ OH 295 CH(CH₃)₂ F NH₂ OH 296 CH₃ Cl NH₂ OH 297 CH₂CH₃ Cl NH₂ OH 298 CH₃ F NH₂ OCH₃ 299 CH₂CH₃ F NH₂ OCH₃ 300 CH(CH₃)₂ F NH₂ OCH₃ 301 CH₃ Cl NH₂ OCH₃ 302 CH₂CH₃ Cl NH₂ OCH₃ 303 CH₃ F NH₂ COOCH₃ 304 CH₂CH₃ F NH₂ COOCH₃ 305 CH(CH₃)₂ F NH₂ COOCH₃ 306 CH₃ Cl NH₂ COOCH₃ 307 CH₂CH₃ Cl NH₂ COOCH₃ 308 CH₃ F NH₂ CH₃ 309 CH₂CH₃ F NH₂ CH₃ 310 CH(CH₃)₂ F NH₂ CH₃ 311 CH₃ Cl NH₂ CH₃ 312 CH₂CH₃ Cl NH₂ CH₃ 313 CH₃ F SH H 314 CH₃ F SH NO₂ 315 CH₃ F SH NH₂ 316 CH₂CH₃ F SH H 317 CH₂CH₃ F SH NO₂ 318 CH₂CH₃ F SH NH₂ 319 CH₃ Cl SH H 320 CH₃ Cl SH NO₂ 321 CH₃ Cl SH NH₂ 322 CH₂CH₃ Cl SH H 323 CH₂CH₃ Cl SH NO₂ 324 CH₂CH₃ Cl SH NH₂ 325 CH₃ H NO₂ H 326 CH₂CH₃ H NO₂ H 327 CH₃ H NH₂ H 328 CH₂CH₃ H NH₂ H 329 CH₃ H NH₂ Br 330 CH₂CH₃ H NH₂ Br 331 CH₃ H NO₂ F 332 CH₂CH₃ H NO₂ F 333 CH₃ H NO₂ Cl 334 CH₂CH₃ H NO₂ Cl 335 CH₃ H NO₂ Br 336 CH₂CH₃ H NO₂ Br 337 CH₃ H NO₂ NH₂ 338 CH₂CH₃ H NO₂ NH₂ 339 CH₃ H OH H 340 CH₂CH₃ H OH H 341 CH₃ H OH NO₂ 342 CH₂CH₃ H OH NO₂ 343 CH₃ H OH NH₂ 344 CH₂CH₃ H OH NH₂ 345 CH₃ H F NO₂ 346 CH₂CH₃ H F NO₂ 347 CH₃ H Cl NO₂ 348 CH₂CH₃ H Cl NO₂ 349 CH₃ H SH NO₂ 350 CH₂CH₃ H SH NO₂ 351 H F Cl H 352 H Cl Cl H 353 H F H F 354 H Cl H Cl 355 H F Br H 356 H F CH₃ H 357 H Cl Br H 358 H F Cl OCH₃ 359 H Cl Cl OCH₃ 360 H F Cl COOCH₂CH₃ 361 H Cl Cl COOCH₃ 362 H F Br COOCH₂CH₃ 363 H F Cl NO₂ 364 H Cl Cl NO₂ 365 H F NO₂ F 366 H F Cl CH₃ 367 H Cl NO₂ Cl 368 H F NH₂ OCH₃ 369 H F Cl NH₂ 370 H Cl Cl NH₂ 371 H F Br NO₂ 372 H F Cl Br 373 H F Cl I 374 H Cl Cl Br 375 H F Cl OH 376 H Cl Cl OH 377 H F NH₂ H 378 H F Cl SH 379 H F OCH₃ H 380 H Cl OCH₃ H 381 H F OH NO₂ 382 H H NH₂ H 383 H H Cl H 384 H H F NO₂ 385 H H Cl NO₂ 386 H H H NH₂

TABLE 7 Compounds of the formula I₃₆ (I₃₆)

Comp. No. R₃ R₄ R₅ R₆ I₃₆.001 CH₃ F F H I₃₆.002 CH₂CH₃ F F H I₃₆.003 CH₃ F F NO₂ I₃₆.004 CH₂CH₃ F F NO₂ I₃₆.005 CH₃ F H F I₃₆.006 CH₂CH₃ F H F I₃₆.007 CH₃ F NO₂ F I₃₆.008 CH₂CH₃ F NO₂ F I₃₆.009 CH₃ F NO₂ OH I₃₆.010 CH₂CH₃ F NO₂ OH I₃₆.011 CH₃ F NO₂ SH I₃₆.012 CH₂CH₃ F NO₂ SH I₃₆.013 CH₃ F NO₂ NH₂ I₃₆.014 CH₂CH₃ F NO₂ NH₂ I₃₆.015 CH₃ Cl Cl NO₂ I₃₆.016 CH₂CH₃ Cl Cl NO₂ I₃₆.017 CH₃ Cl H Cl I₃₆.018 CH₂CH₃ Cl H Cl I₃₆.019 CH₃ Cl NO₂ Cl I₃₆.020 CH₂CH₃ Cl NO₂ Cl I₃₆.021 CH₃ Cl NO₂ OH I₃₆.022 CH₂CH₃ Cl NO₂ OH I₃₆.023 CH₃ Cl NO₂ SH I₃₆.024 CH₂CH₃ Cl NO₂ SH I₃₆.025 CH₃ Cl NO₂ NH₂ I₃₆.026 CH₂CH₃ Cl NO₂ NH₂ I₃₆.027 CH₃ F NO₂ OCH₃ I₃₆.028 CH₂CH₃ F NO₂ OCH₃ I₃₆.029 CH₃ Cl NO₂ OCH₃ I₃₆.030 CH₂CH₃ Cl NO₂ OCH₃ I₃₆.031 CH₃ F NH₂ OCH₃ I₃₆.032 CH₂CH₃ F NH₂ OCH₃ I₃₆.033 CH₃ Cl NH₂ OCH₃ I₃₆.034 CH₂CH₃ Cl NH₂ OCH₃ I₃₆.035 CH₃ F NH₂ OH I₃₆.036 CH₂CH₃ Cl NH₂ OH I₃₆.037 CH₂CH₃ F NH₂ OH I₃₆.038 CH₃ Cl NH₂ OH I₃₆.039 CH₃ F Cl NH₂ I₃₆.040 CH₂CH₃ F Cl NH₂ I₃₆.041 CH₃ Cl Cl NH₂ I₃₆.042 CH₂CH₃ Cl Cl NH₂ I₃₆.043 CH₃ F Br NO₂ I₃₆.044 CH₂CH₃ F Br NO₂ I₃₆.045 CH₃ F CH₃ NO₂ I₃₆.046 CH₂CH₃ F CH₃ NO₂ I₃₆.047 CH₃ F Br NH₂ I₃₆.048 CH₂CH₃ F Br NH₂ I₃₆.049 CH₃ F CH₃ NH₂ I₃₆.050 CH₂CH₃ F CH₃ NH₂ I₃₆.051 CH₃ F OH NO₂ I₃₆.052 CH₃ Cl OH NO₂ I₃₆.053 CH₂CH₃ F OH NO₂ I₃₆.054 CH₂CH₃ Cl OH NO₂ I₃₆.055 CH₃ F SH NO₂ I₃₆.056 CH₃ Cl SH NO₂ I₃₆.057 CH₂CH₃ F SH NO₂ I₃₆.058 CH₂CH₃ Cl SH NO₂ I₃₆.059 CH₃ F OH NH₂ I₃₆.060 CH₃ Cl OH NH₂ I₃₆.061 CH₂CH₃ F OH NH₂ I₃₆.062 CH₂CH₃ Cl OH NH₂ I₃₆.063 CH₃ F SH NH₂ I₃₆.064 CH₃ Cl SH NH₂ I₃₆.065 CH₂CH₃ F SH NH₂ I₃₆.066 CH₂CH₃ Cl SH NH₂ I₃₆.067 CH₃ F NO₂ Br I₃₆.068 CH₂CH₃ F NO₂ Br I₃₆.069 CH₃ F NO₂ COOH I₃₆.070 CH₂CH₃ F NO₂ COOH I₃₆.071 CH₃ Cl NO₂ Br I₃₆.072 CH₂CH₃ Cl NO₂ Br I₃₆.073 CH₃ Cl NO₂ COOH I₃₆.074 CH₂CH₃ Cl NO₂ COOH I₃₆.075 CH₃ F NH₂ COOH I₃₆.076 CH₂CH₃ F NH₂ COOH I₃₆.077 CH₃ Cl NH₂ COOH I₃₆.078 CH₂CH₃ Cl NH₂ COOH I₃₆.079 CH₃ H F H I₃₆.080 CH₂CH₃ H F H I₃₆.081 CH₃ H F NO₂ I₃₆.082 CH₂CH₃ H F NO₂ I₃₆.083 CH₃ H Cl H I₃₆.084 CH₂CH₃ H Cl H I₃₆.085 CH₃ H Cl NO₂ I₃₆.086 CH₂CH₃ H Cl NO₂ I₃₆.087 CH₃ H NO₂ H I₃₆.088 CH₂CH₃ H NO₂ H I₃₆.089 CH₃ H NO₂ F I₃₆.090 CH₂CH₃ H NO₂ F I₃₆.091 CH₃ H NO₂ Cl I₃₆.092 CH₂CH₃ H NO₂ Cl I₃₆.093 CH₃ H NO₂ OH I₃₆.094 CH₂CH₃ H NO₂ OH I₃₆.095 CH₃ H NH₂ H I₃₆.096 CH₂CH₃ H NH₂ H I₃₆.097 CH₃ H NO₂ NH₂ I₃₆.098 CH₂CH₃ H NO₂ NH₂ I₃₆.099 CH₃ H NH₂ H I₃₆.100 CH₂CH₃ H NH₂ H I₃₆.101 CH₃ F Cl OH I₃₆.102 CH₂CH₃ F Cl OH I₃₆.103 CH₃ Cl Cl OH I₃₆.104 CH₂CH₃ Cl Cl OH I₃₆.105 CH₃ H Cl OH I₃₆.106 CH₂CH₃ H Cl OH I₃₆.107 CH₃ F Cl NO₂ I₃₆.108 CH₂CH₃ F Cl NO₂ I₃₆.109 CH₃ F Cl I I₃₆.110 CH₂CH₃ F Cl I I₃₆.111 CH₃ Cl Cl I I₃₆.112 CH₂CH₃ Cl Cl I

TABLE 8 Compounds of the formulae V₃, V₄, II₂ and III₂ (V₃)

(V₄)

(II₂)

(III₂)

Comp. No. V_(n) or II₂ and III₂ n = 3 or 4 R₃ R₄ R₆₁ 001 H F H 002 CH₃ F H 003 CH₂CH₃ F H 004 CH(CH₃)₂ F H 005 H Cl H 006 CH₃ Cl H 007 CH₂CH₃ Cl H 008 CH(CH₃)₂ Cl H 009 CH₂CCH F H 010 H F CH(CH₃)₂ 011 CH₃ F CH(CH₃)₂ 012 CH₂CH₃ F CH(CH₃)₂ 013 CH(CH₃)₂ F CH(CH₃)₂ 014 H Cl CH(CH₃)₂ 015 CH₃ Cl CH(CH₃)₂ 016 CH₂CH₃ Cl CH(CH₃)₂ 017 CH(CH₃)₂ Cl CH(CH₃)₂ 018 H F CH₂CHCH₂ 019 CH₃ F CH₂CHCH₂ 020 CH₂CH₃ F CH₂CHCH₂ 021 CH(CH₃)₂ F CH₂CHCH₂ 022 H Cl CH₂CHCH₂ 023 CH₃ Cl CH₂CHCH₂ 024 CH₂CH₃ Cl CH₂CHCH₂ 025 CH(CH₃)₂ Cl CH₂CHCH₂ 026 CH₃ F CH₂CCH 027 CH₂CH₃ F CH₂CCH 028 CH(CH₃)₂ F CH₂CCH 029 CH₃ Cl CH₂CCH 030 CH₂CH₃ Cl CH₂CCH 031 CH(CH₃)₂ Cl CH₂CCH 032 CH₃ F CH₂C₆H₅ 033 CH₂CH₃ F CH₂C₆H₅ 034 H F CH₂COOH 035 CH₃ F CH₂COOH 036 CH₂CH₃ F CH₂COOH 037 CH(CH₃)₂ F CH₂COOH 038 H Cl CH₂COOH 039 CH₃ Cl CH₂COOH 040 CH₂CH₃ Cl CH₂COOH 041 CH(CH₃)₂ Cl CH₂COOH 042 CH₃ F CH(CH₃)COOCH₃ 043 CH₂CH₃ F CH(CH₃)COOCH₃ 044 CH(CH₃)₂ F CH(CH₃)COOCH₃ 045 CH₃ Cl CH(CH₃)COOCH₃ 046 CH₂CH₃ Cl CH(CH₃)COOCH₃ 047 CH(CH₃)₂ Cl CH(CH₃)COOCH₃ 048 H H H 049 CH₃ H H 050 CH₂CH₃ H H 051 CH(CH₃)₃ H H 052 H H CH₂COOH 053 CH₃ H CH₂COOH 054 CH₂CH₃ H CH₂COOH 055 CH(CH₃)₂ H CH₂COOH

TABLE 9 Compounds of the formulae II₃, V₅, V₆ and III₃ (II₃)

(V₅)

(V₆)

(III₃)

Comp. No. V_(n) or II₃ and III₃ n = 5 or 6 R₃ R₄ R₆₁ 001 H F H 002 CH₃ F H 003 CH₂CH₃ F H 004 CH(CH₃)₂ F H 005 H Cl H 006 CH₃ Cl H 007 CH₂CH₃ Cl H 008 CH(CH₃)₂ Cl H 009 H F CH(CH₃)₂ 010 CH₃ F CH(CH₃)₂ 011 CH₂CH₃ F CH(CH₃)₂ 012 CH(CH₃)₂ F CH(CH₃)₂ 013 H Cl CH(CH₃)₂ 014 CH₃ Cl CH(CH₃)₂ 015 CH₂CH₃ Cl CH(CH₃)₂ 016 CH(CH₃)₂ Cl CH(CH₃)₂ 017 H F CH₂CHCH₂ 018 CH₃ F CH₂CHCH₂ 019 CH₂CH₃ F CH₂CHCH₂ 020 CH(CH₃)₂ F CH₂CHCH₂ 021 H Cl CH₂CHCH₂ 022 CH₃ Cl CH₂CHCH₂ 023 CH₂CH₃ Cl CH₂CHCH₂ 024 CH(CH₃)₂ Cl CH₂CHCH₂ 025 CH₃ F CH₂CCH 026 CH₂CH₃ F CH₂CCH 027 CH(CH₃)₂ F CH₂CCH 028 CH₃ Cl CH₂CCH 029 CH₂CH₃ Cl CH₂CCH 030 CH(CH₃)₂ Cl CH₂CCH 031 H F CH₂COOH 032 CH₃ F CH₂COOH 033 CH₂CH₃ F CH₂COOH 034 CH(CH₃)₂ F CH₂COOH 035 H Cl CH₂COOH 036 CH₃ Cl CH₂COOH 037 CH₂CH₃ Cl CH₂COOH 038 CH(CH₃)₂ Cl CH₂COOH 039 CH₃ F CH(CH₃)COOCH₃ 040 CH₂CH₃ F CH(CH₃)COOCH₃ 041 CH(CH₃)₂ F CH(CH₃)COOCH₃ 042 CH₃ Cl CH(CH₃)COOCH₃ 043 CH₂CH₃ Cl CH(CH₃)COOCH₃ 044 CH(CH₃)₂ Cl CH(CH₃)COOCH₃ 045 H H H 046 CH₃ H H 047 CH₂CH₃ H H 048 CH(CH₃)₂ H H 049 H H CH₂COOH 050 CH₃ H CH₂COOH 051 CH₂CH₃ H CH₂COOH 052 CH(CH₃)₂ H CH₂COOH

TABLE 10 Compounds of the formulae III₄, III₅ and III₆ (III₄)

(III₅)

(III₆)

Comp. No. III_(n) n = 4-6 R₃ R₄ R₅ R₇₂ 001 CH₃ H Cl CH₃ 002 CH₃ H Cl CH₂OH 003 CH₃ H Cl COOH 004 CH₃ F Cl CH₃ 005 CH₃ F Cl CH₂OH 006 CH₃ F Cl CH₂Cl 007 CH₃ F Cl COOH 008 CH₃ F Cl COOCH₃ 009 CH₃ F Br CH₂OH 010 CH₃ F Br COOH 011 C₂H₅ F Cl CH₃ 012 C₂H₅ F Cl CH₂OH 013 CH₃ Cl Cl CH₃ 014 CH₃ Cl Cl CH₂OH 015 CH₃ Cl Cl COOH

TABLE 11 Prepared compounds from the above Tables 1-10 together with physicochemical data. Comp No. Physicochemical data I₁.001 m.p. 152-153° C. I₁.006 m.p. 155-156° C. I₁.027 m.p. 145-146° C. I₁.108 oil (recem.) I₁.118 resin I₁.130 m.p. 240-242° C. I₁.134 m.p. 127-128° C. I₁.140 m.p. 88-89° C. I₁.151 m.p. 129-131° C. I₁.159 m.p. 57-58° C. I₁.219 m.p.57-58° C. I₁.220 m.p. 183-184° C. I₁.221 resin I₁.222 m.p. 57-58° C. I₁.223 m.p. 151-152° C. I₃.001 resin I₃.006 m.p. 227-228° C. I₃.027 m.p. 256-257° C. I₃.130 m.p. 179-185° C. I₃.140 m.p. 92-93° C. I₃.151 m.p. 149-151° C. I₃.159 oil I₃.219 resin I₅.001 m.p. 174-175° C. I₆.001 m.p. 163-164° C. I₃₆.015 m.p. 119-120° C. I₃₆.017 m.p. 113-114° C. I₃₆.019 m.p. 234-235° C. I₃₆.033 m.p. 243-244° C. I₃₆.039 m.p. 133-134° C. I₃₆.041 m.p. 90-91° C. I₃₆.101 m.p. 172-173° C. I₃₆.103 m.p. 263-265° C. I₃₆.107 m.p. 137-138° C. I₃₆.109 m.p. 144-145° C. V₁.071 m.p. 135-137° C. V₁.358 solid V₂.071 solid II₁.071 m.p. 224-226° C.

Formulation Examples of Active Ingredients of the Formula I (%=per cent by weight)

F1. Emulsion concentrates a) b) c) d) Active ingredient of Tables 1-5 and 7  5% 10% 25% 50% Calcium dodecylbenzenesulfonate  6%  8% 6% 8% Castor oil polyglycol ether  4% — 4% 4% (36 mol of EO) Octylphenol polyglycol ether —  4% — 2% (7-8 mol of EO) Cyclohexanone — — 10% 20% Aromatic hydrocarbon mixture C₉-C₁₂ 85% 78% 55% 16%

Emulsions of any desired concentration can be prepared from such concentrates by diluting them with water.

F2. Solutions a) b) c) d) Active ingredient of Tables 1-5 and 7  5% 10% 50% 90% 1-methoxy-3-(3-methoxypropoxy) — 20% 20% — propane Polyethylene glycol MW 400 20% 10% — — N- methyl-2-pyrrolidone — — 30% 10% Aromatic hydrocarbon mixture C₉-C₁₂ 75% 60% — —

The solutions are suitable for use in the form of microdrops.

F3. Wettable powders a) b) c) d) Active ingredient of Tables 1-5 and 7  5% 25% 50% 80% Sodium lignosulfonate  4% —  3% — Sodium lauryl sulfate  2%  3% —  4% Sodium diisobutylnaphthalenesulfonate —  6%  5%  6% Octylphenyl polyglycol ether (7-8 Mol EO) —  1%  2% — Highly disperse silica  1%  3%  5% 10% Kaolin 88% 62% 35% —

The active ingredient is mixed thorougly with the additives and the mixture is ground thoroughly in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentration.

F4. Coated granules a) b) c) Active ingredient of Tables 1-5 and 7 0.1% 5% 15% Hghly-disperse silica 0.9% 2% 2% Inorganic carrier material ( 0.1-1 mm), 99.0% 93% 83% for example CaCO₃ or SiO₂

The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated in vacuo.

F5. Coated granules a) b) c) Active ingredient of Tables 1-5 and 7 0.1% 5% 15% Polyethylene glycol MW 200 1.0% 2% 3% Highiy disperse silica 0.9% 1% 2% Inorganic carrier material ( 0.1-1 mm), 98.0% 92% 80% for example CaCO₃ or SiO₂

In a mixer, the finely ground active ingredient is applied uniformly to the carrier material which has been moistened with polyethylene glycol. In this manner, dust-free coated granules are obtained.

F6. Extruder granules a) b) c) d) Active ingredient of Tables 1-5 and 7 0.1% 3% 5% 15% Sodium lignosulfonate 1.5% 2% 3% 4% Carboxymethylcellulose 1.4% 2% 2% 2% Kaolin 97.0% 93% 90% 79%

The active ingredient is mixed with the additives, and the mixture is ground and moistened with water. This mixture is extruded and subsequently dried in a stream of air.

F7. Dusts a) b) c) Active ingredient of Tables 1-5 and 7 0.1% 1% 5% Talc 39.9% 49% 35% Kaolin 60.0% 50% 60%

Ready-to-use dusts obtained by mixing the active ingredient with the carriers and grinding the mixture on a suitable mill.

F8. Suspensions concentrates a) b) c) d) Active ingredient of Tables 1-5 and 7 3%   10%  25% 50%  Ethylene glycol 5%   5%   5% 5%   Nonylphenyl polyglycol ether —   1% 2% — (15 mols of EO) Sodium lignosulfonate 3%   3%   4% 5%   Carboxymethylcellulose 1%   1%   1% 1%   37% aqueous formladehyde solution 0.2% 0.2% 0.2% 0.2% Silicone oil emulsion 0.8% 0.8% 0.8% 0.8% Water 87%  79%  62% 38% 

The finely ground active ingredient is mixed intimately with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by diluting it with water.

Biological Examples

EXAMPLE B1

Herbicidal Action Before Emergence of the Plants (Pre-emergence Action)

Monocotyledoneous and dicotyledoneous test plants are grown in standard soil in plastic pots. Immediately after sowing, the test substances are sprayed on in the form of an aqueous suspension or emulsion, prepared from a 25% emulsion concentrate (Example F1, c)), which corresponds to a dosage of 500 g of a.i./ha (500 l of water/ha). The test plants are subsequently grown in the greenhouse under optimal conditions. After a test period of 3 weeks, the experiment is evaluated on a nine-step scale (1=complete damage, 9=no action). Score figures of 1 to 4 (in particular 1 to 3) denote a good to very good herbicidal action.

Test plants: Avena, Setaria, Solanum, Stellaria, Ipomoea.

The compounds according to the invention have good herbicidal activity.

Examples of the good herbicidal activity of the compounds of the formula I are given in Table B1.

TABLE B1 Pre-emergence action: Active ingre- Test plant: dient So- Dose No. Avena Setaria lanum Stellaria Ipomoea [g of a.i./ha] I₁.001 4 1 1 6 3 500 I₁.006 4 1 1 1 4 500 I₁.027 3 2 1 1 4 500 I₁.140 3 1 2 1 4 500 I₃.027 6 1 1 2 6 500 I₅.001 6 1 1 7 6 500

The same results are obtained when the compounds of the formula I are formulated in accordance with Examples F2 to F8.

EXAMPLE B2

Post-emergence Herbicidal Action

In the greenhouse, monocotyledoneous and dicotyledoneous test plants are grown in standard soil in plastic pots and, in the 4- to 6-leaf stage, sprayed with an aqueous suspension or emulsion of the test substances of the formula I, prepared from a 25% emulsion concentrate (Example F1, c)), which corresponds to a dosage of 500 g of a.i./ha (500 l of water/ha). The test plants are subsequently grown on in the greenhouse under optimal conditions. After a test period of approximately 18 days, the experiment is evaluated on a nine-step scale (1=complete damage, 9=no action). Score figures of 1 to 4 (in particular 1 to 3) denote a good to very good herbicidal action.

Test plants: Setaria, Sinapis, Solanum, Stellaria, Ipomoea.

In this test too, the compounds of the formula I show a potent herbicidal activity.

Examples of the good herbicidal activity of the compounds of formula I are given in Table B2.

TABLE B2 Post-emergence action: Dose Test plant: Setaria Sinapis Solanum Stellaria Ipomoea [g of a.i./ha] Active ingredient No. I₁, 001 3 4 2 5 1 500 I₁, 006 2 3 1 3 1 500 I₁, 027 3 3 1 1 1 500 I₁, 122 4 1 1 1 1 500 I₁, 130 3 1 1 1 1 500 I₁, 134 5 3 1 1 1 500 I₁, 140 2 4 1 1 1 500 I₁, 151 3 1 i 1 1 500 I₃, 027 6 3 1 3 3 500 I₅, 001 6 7 1 7 1 500

The same results are obtained when the compounds of the formula I are formulated in accordance with Examples F2 to F8. 

What is claimed is:
 1. A compound of the formula I

in which R₁ is C₁-C₄alkyl; R₂ is cyano; R₃ is hydrogen, C₁-C₄alkyl, C₁-C₄haloalkyl, C₃- or C₄alkenyl, C₃- or C₄alkynyl, C₃-C₈haloalkenyl, NC—CH₂—, HOC(O)—CH₂— or C₁-C₄alkoxy-C(O)—CH₂—; W is a group W₁

R₄ is fluorine, chlorine, or bromine; R₅ is halogen; R₆ is OR₂₀; R₂₀ is C₃-C₈alkynyl; or an agronomically acceptable salt or steroisomer thereof.
 2. A compound according to claim 1 in which R₁ is methyl and R₃ is methyl or ethyl.
 3. A compound according to claim 2 in which R₄ is fluorine.
 4. A compound according to claim 2 in which R₄ is chlorine.
 5. A compound according to claim 1 in which R₅ is chlorine or bromine.
 6. A compound according to claim 1, of the formula I_(a)

in which W and R₁ to R₃ are as defined in claim
 1. 7. A compound according to claim 6 in which R₁ is methyl; R₂ is cyano; and R₃ is methyl or ethyl.
 8. A compound according to claim 7 in which W is a group

and R₄ is fluorine or chlorine.
 9. A process for the preparation of a compound of the formula I

in which W, R₁ and R₃ are as defined in claim 1; and R₂ is cyano; which comprises a) dehydrating a compound of the formula IIa or IIb

in which W, R₁ and R₃ are as defined above; or b) first diazotizing a compound of the formula IIIa or IIIb

in which W, R₁ and R₃ are as defined above and subsequently reacting the diazonium salt formed with a salt of the formula X M⁺CN⁻  (X) in which M⁺ is an alkali metal, alkaline earth metal or transition metal ion; or c) reacting a compound of the formula IVa or IVb

in which W, R₁ and R₃ are as defined above with hydroxylamine or a salt thereof and dehydrating the oxime formed as an intermediate; or d) reacting a compound of the formula Va or Vb

in which W, R₁ and R₃ are as defined in claim 1 and R₈₁ is C₁-C₄alkyl, C₃- or C₄alkenyl or benzyl with dimethylaluminium amide in the presence of an inert organic solvent.
 10. A herbicidal and plant growth-inhibiting composition which comprises a herbicidally effective content of a compound of the formula 1 of claim 1 and an inert carrier.
 11. A composition according to claim 10 which comprises between 0.1% and 95% of active ingredient of the formula I.
 12. A method of controlling undesirable plant growth, which comprises applying a herbicidally effective amount of an active ingredient of the formula 1 of claim 1 or a composition comprising this active ingredient to the crops of the useful plants or their environment.
 13. A method according to claim 12, which comprises applying an amount of active ingredients of between 0.001 and 4 kg per hectare.
 14. A method of inhibiting plant growth, which comprises applying an effective amount of an active ingredient of the formula 1 of claim 1 or of a composition comprising this active ingredient to the plants or their environment.
 15. A method according to claim 12, wherein the crops of useful plants are cereals, maize, rice, cotton, soya, oilseed rape, sorghum, sugar cane, sugar beet, sunflowers, vegetables and fodder plants. 